Compositions containing antimicorbial agents in combination with stabilizers

ABSTRACT

Composition of an antimicrobial agent and an antioxidant having improved antimicrobial activity compared to the antimicrobial agent alone. The preferred environment of the invention is a composition of a thermoplastic resin, an antioxidant, and an antimicrobial agent, the latter two being compatible with the resin. The resin composition can contain other usual additives, and can be melt processed at an elevated temperature to form articles such as films or fibers having improved antimicrobial activity. A method for improving the efficacy of an antimicrobial agent by combining it with an antioxidant is disclosed. A method for melt-processing a resin composition containing an antimicrobial material is also disclosed, wherein the resin composition includes an antioxidant. The inventors have thus discovered and solved the problem of oxidation of an antimicrobial composition, particularly a resin composition containing an antimicrobial agent, which arises when the composition is processed at elevated temperatures, as are typically encountered when forming a fiber or film of the composition.

TECHNICAL FIELD

The present invention relates to thermoplastic articles and compositions containing antimicrobial agents and to novel stabilizers for antimicrobial agents.

BACKGROUND ART

It is well known that antimicrobial agents can be incorporated into thermoplastic materials during fabrication so the resulting thermoplastic articles will resist microbial growth. Thermoplastic compounds which are candidates for treatment include materials such as polyamides (nylon 6 or 6,6), polyvinyl chloride (with or without plasticizing agents), polyolefins, polyurethanes, polyethylene terephthalate (polyester), styrene-butadiene rubbers, other elastomers, etc. Antimicrobial agents which are candidates for incorporation into such thermoplastic materials include, but are not limited to, phenoxarsines (including bisphenoxarsines), phenarsazines (including bisphenarsazines), maleimides, isoindole dicarboximides having a sulfur atom bonded to the nitrogen atom of the dicarboximide group, halogenated aryl alkanols, isothiazolinone compounds, and organotin compounds. Others have also been used.

The known microbiocidal phenoxarsine and phenarsazine compounds include compounds represented by the formulas: ##STR1## where X is halogen or thiocyanate, Y is oxygen or sulfur, Z is oxygen or NH, R₁ is halogen, lower alkyl (having from 1 to about 6 carbon atoms), or thiocyanate, and n is from 1 to 4 inclusive. Examples of these phenoxarsines and phenarsazines include, but are not limited to:

10-chlorophenoxarsine;

10-iodophenoxarsine;

10-bromophenoxarsine;

4-methyl-10-chlorophenoxarsine;

2-tert-butyl-10-chlorophenoxarsine;

1,4-dimethyl-10-chlorophenoxarsine

2-methyl-8,10-dichlorophenoxarsine;

1,3,10-trichlorophenoxarsine;

2,6,10-trichlorophenoxarsine;

2,8,10-trichlorophenoxarsine;

1,2,4,10-tetrachlorophenoxarsine;

1,2,4,10-thiocyanatophenoxarsine;

10-thiocyanatophenoxarsine;

10,10'-thiobisphenoxarsine;

10,10'-oxybisphenarsazine;

10,10'-thiobisphenarsazine; and

10,10'-oxybisphenoxarsine (OBPA).

Many of these materials are described in U.S. Pat. No. 3,288,674, issued to Yeager Nov. 19, 1966.

The microbiocidal maleimide compounds are exemplified by N-(2-methylnaphthyl)maleimide.

The microbiocidal isoindole dicarboximides having a sulfur atom bonded to the nitrogen atom of the dicarboximide group contain at least one group having the structure: ##STR2## wherein the hexagonal ring can have one to three sites of ring saturation.

Particular isoindole dicarboximides are the following: ##STR3##

An example of a isothiazolinone compound which has been found useful is 2-(n-octyl-4-isothiazolin-3-one).

Other known antimicrobial agents are: bis(tri-n-butyl tin)oxide (TBTO); pentachlorophenol and its salts; zinc Omadine (a zinc derivative of pyridinethione sold by Olin Chemicals, Stamford, Conn.); 2'-hydroxy-2,4,4'-trichlorodiphenylether (Irgasan DP-300, sold by Ciba-Geigy Corporation, Plastics and Additives Division, Hawthorne, N.Y.); 2,4,5,6-tetrachloroisophthalonitrile (Daconil 2787, sold by Diamond Alkali Company, Cleveland, Ohio); and 2-(4-thiazolyl)benzimidazole (trade name Tektamer 100, sold by the Calgon Division of Merck & Co., Inc., Rahway, N.J.).

In all of these combinations of an antimicrobial agent and a thermoplastic material, the antimicrobial agent must: (1) have sufficient heat stability to avoid being destroyed or losing potency during fabrication; (2) not react with the thermoplastic resin nor any of its additives at elevated processing temperatures and other conditions; and (3) not become volatilized. In addition, the antimicrobial control agent should not impart undesirable features (odor, embrittlement) to the resin at use concentrations. A final requirement is that the composition effectively control microbial growth throughout the intended life of the finished article.

Synthetic fiber manufacture subjects the fiber composition to extremely rigorous conditions. For example, the fiber composition is melted and held at an elevated temperature prior to spinning. When spun, the composition is subjected to extremely high pressures and is further heated by the friction of extrusion. The extruded filaments are then cooled by ventilating them with air. The filaments have a large surface to volume ratio, and thus the composition is extensively exposed to atmospheric oxygen while cooling.

U.S. Pat. No. 3,345,341 claims thermoplastic compositions formed by blending an antimicrobial agent at a suitable ratio with chips of the polymer form prior to fabrication. The compositions are then spun into fibers. The degradation problem and possible solutions are not discussed.

U.S. Pat. No. 2,919,200 (Dubic, et al.) teaches incorporating a bacteriostatic agent in a thermoplastic composition, but simply specifies that the bacteriostatic agent should have a decomposition temperature above the molding temperature of the plastic. Many existing antimicrobial agents do not meet this criterion.

Similarly, U.S. Pat. No. 3,959,556 (Morrison) describes the preparation of synthetic fibers which incorporate an antimicrobial agent, and claims antimicrobial properties are possessed by blends of the treated synthetic fiber with naturally occurring fibers.

U.S. Pat. No. 3,279,986 (Hyman) describes preparation of a thermoplastic sheet material incorporating an antimicrobial agent. The specific antimicrobial agents clamed also are claimed to improve the thermal susceptibility of the sheet material. ("Thermal susceptibility" refers to the well known off-color that results from heating polyvinyl chloride resin materials.)

A weakness of all these patents is their failure to disclose that the antimicrobial agent present in the finished material often lacks some or all of its potency as a result of degradation during processing.

For example, if 500 parts per million (ppm) of OBPA is blended into a nylon composition, which is formed into fiber using conventional melt-spinning technology, only about 100 ppm of active OBPA will be present in the fiber.

This degradation has two important disadvantages. First, much of the antimicrobial agent is wasted so more of the agent must be incorporated in the chosen composition to provide a desired level of performance. Second, the decomposition products of the antimicrobial agent may be more easily released from a thermoplastic composition than the active agent. For example, when nylon fibers containing OBPA are vat dyed, much of the decomposition product (phenoxyarsenic acid) formed as a result of fiber fabrication migrates into the dye bath, necessitating removal before the dye effluent is released into the environment. If the amount of decomposition of OBPA during fiber formulation were reduced, the leaching of the phenoxyarsenic acid from fibers would be reduced.

Further, some known biological agents are not selected in these patents because the omitted agents are known to be insufficiently resistant to thermal inactivation.

The literature discloses using antioxidants in polymeric plastic compositions. There is a wide spectrum of needs for such antioxidants in different polymers and plastic compounds. For example, some resin compositions cannot be fabricated at all without antioxidants, while polyvinyl chloride compositions and polyamide (such as nylon) compositions do not benefit substantially from inclusion of an antioxidant except during high-temperature fabrication.

The following materials are known to act as antioxidants for plastic compositions:

    ______________________________________                                         MONOPHENOLS                                                                    ______________________________________                                         1. 2,6-Di-t-butyl-p-cresol or                                                  2,6-Di-t-butyl-4-methylphenol                                                   ##STR4##          Mole Weight 220 White powder, flakes, granules or                              pellets Melt Point 69-70° C. Specific Gravity                           1.04-1.05                                                   ______________________________________                                         TRADENAME          SUPPLIER                                                    ______________________________________                                         BHT                Koppers                                                     CAO-1              Sherwin-Williams                                            CAO-3              Sherwin-Williams                                            DBPC               Koppers                                                     DBPC-80 (1)        Koppers                                                     Ionol              Shell                                                       Ionol CP           Shell                                                       Lowinox BHT        Lowi                                                        Naugard BHT        Uniroyal                                                    Permanax BHT       Vulnax                                                      Sustane BHT        UOP                                                         Sustane 1-F        UOP                                                         Vanox PC           Vanderbilt                                                  Vanox PC-X         Vanderbilt                                                  Vulkanox KB        Mobay                                                       ______________________________________                                          (1) 80%                                                                  

    2. Styrenated phenol                                                            ##STR5##             Viscous straw colored liquid Specific Gravity 1.08       General purpose non-staining antioxidant                                       used in rubber and latex.                                                      ______________________________________                                         TRADENAME             SUPPLIER                                                 ______________________________________                                         WINGSTAY S            GOODYEAR                                                 WINGSTAY S Powder (1) GOODYEAR                                                 Antioxidant SP (2)    Harwick                                                  Lowinox P24S          Lowi                                                     Naugard SP            Uniroyal                                                 Naugard SP Powder (3) Uniroyal                                                 Nevastain 21          Neville                                                  Nevastain 2170 (3)    Neville                                                  Permanax SP (4)       Vulnax                                                   Permanax SP(L)        Vulnax                                                   Stabilite SP 49-464 (5)                                                                              Reichhold                                                Styrenated Phenol     Ferro/Productol                                          Vanox 102             Vanderbilt                                               Vanox 1002            Vanderbilt                                               ______________________________________                                          (1) 65% Active on inert carrier                                                (2) Active concentration not listed  Specific Gravity 1.56                     (3) 70% Active on inert carrier  Specific Gravity 1.32                         (4) 60% Active on inert carrier                                                (5) Listed as `polymeric styrenated                                      

    3. 2- and 3-t-Butyl-4-hydroxyanisole or                                        2- and 3-t-Butyl-4-methoxyphenol                                                ##STR6##             Mole Weight 180 White or off-white tablets or                                  pellets Melt Point 48-57° C. Specific                                   Gravity 1.04                                             General purpose antioxidant                                                    frequently used in foods.                                                      ______________________________________                                         TRADENAME             SUPPLIER                                                 ______________________________________                                         Sustane BHA           UOP                                                      Tenox BHA             Eastman                                                  ______________________________________                                         4. Alkylated hindered phenols                                                   ##STR7##        Viscous liquids varying in color from pale straw to                            brown                                                         R's may be methyl or other alkyl groups, the larger ones usually               being tertiary. Frequently more than one type of group is present.             General purpose antioxidants and polymer stabilizers for rubber                and plastics. These generally have good color and stain                        ______________________________________                                         properties.                                                                                                   SPECIFIC                                        TRADENAME        SUPPLIER      GRAVITY                                         ______________________________________                                         WINGSTAY C       GOODYEAR      1.01                                            WINGSTAY T       GOODYEAR      0.91                                            WINGSTAY V       GOODYEAR      1.02                                            Antioxidant 431  Uniroyal      1.08                                            CAO-42           Sherwin-Williams                                                                             0.93                                            Cyanox LF        Cyanamid      1.06                                            Cyanox 251 (1)   Cyanamid      1.39                                            Cyanox 1735      Cyanamid      0.90                                            Ethyl Antioxidant 733                                                                           Ethyl         0.94                                            Ethyl Antioxidant 735                                                                           Ethyl         0.95                                            Hydrochem AO-535C                                                                               Continental   0.90                                                             Products                                                      Lowinox P24A     Lowi                                                          Naugard 431      Uniroyal      1.08                                            Permanax WSL     Vulnax        1.00                                            Permanax WSL Powder                                                                             Vulnax        1.26                                            Prodox 246       Ferro/Productol                                                                              0.931                                           Prodox 340       Ferro/Productol                                                                              0.958                                           Prodox 345       Ferro/Productol                                                                              0.959                                           Stabilite White Powder 49-454                                                                   Reichhold     1.32                                            Stabilite White Liquid 49-455                                                                   Reichhold     0.91                                            Stabilite 49-470 (2)                                                                            Reichhold                                                     Stabiwhite Powder                                                                               CP Hall       1.32                                            Uvinox 1494      GAF           0.90                                            Vanox 100        Vanderbilt    1.03                                            Vanox 100 Powder Vanderbilt    1.37                                            Vulkanox DS/F (3)                                                                               Mobay         1.3                                             ______________________________________                                          (1) Cream white powder  contains an inert carrier                              (2) White powder                                                               (3) Contains 50% inorganic filler                                        

    5. 4-(Hydroxymethyl)-2,6-di-                                                   t-butylphenol                                                                   ##STR8##          Mole Weight 236.4 Off-white crystalline powder Melt                            Point 138° C.                                        ______________________________________                                         TRADENAME          SUPPLIER                                                    ______________________________________                                         Ethyl Antioxidant 754                                                                             Ethyl                                                       ______________________________________                                         6. `Fortified` hindered phenol                                                 (Structured not disclosed)                                                                        White powder                                                                   Melt Point 95° C. min.                                                  Specific Gravity 1.30                                       General purpose phenolic antioxidant used in compounding                       where color and staining are critical.                                         ______________________________________                                         TRADENAME          SUPPLIER                                                    ______________________________________                                         Vanox ZS           Vanderbilt                                                  ______________________________________                                         7. 2,6-Di-t-butyl-4-sec-butylphenol                                             ##STR9##          Mole Weight 262 Amber liquid Specific Gravity               ______________________________________                                                            0.90                                                        TRADENAME          SUPPLIER                                                    ______________________________________                                         Isonox 132         Schenectady                                                 Vanox 1320         Vanderbilt                                                  ______________________________________                                    

    __________________________________________________________________________     BISPHENOLS AND THIOBISPHENOLS                                                  __________________________________________________________________________     1. 2,2'-Methylenebis(6-t-butyl-p-cresol) or                                    2,2'-Methylenebis(4-methyl-6-t-butylphenol)                                     ##STR10##                Mole Weight 341 White or light colored powder                                  Melt Point 133° C. Specific Gravity                                     1.04-1.08                                            Antioxidant for rubber compounding. Some use in latex and plastics.            Essentially non-staining, but can cause slight pink discoloration.             TRADE NAME             SUPPLIER                                                __________________________________________________________________________     Antioxidant MBP-5      Aceto                                                   CAO-5                  Sherwin-Williams                                        CAO-14                 Sherwin-Williams                                        Cyanox 2246            Cyanamid                                                Lowinox 22M46          Lowi                                                    Oxy-Chek 114           Ferro                                                   Santowhite PC          Monsanto                                                Vanox 2246             Vanderbilt                                              Vulkanox BKF           Mobay                                                   __________________________________________________________________________     2. 2,2'-Methylenebis(4-ethyl-6-t-butylphenol)                                   ##STR11##                 Mole Weight 369 White to cream powder Melt                                    Point 119-125° C. Specific Gravity 1.10       General purpose antioxidant weaker than (B-1), but less discoloring.           TRADE NAME             SUPPLIER                                                __________________________________________________________________________     Cyanox 425             Cyanamid                                                __________________________________________________________________________     3. 4,4'-Methylenebis(2,6-di-t-butylphenol)                                      ##STR12##                Mole Weight 424 Light yellow crystalline powder                                elt Point 154-155° C. Specific Gravity                                  1.01                                                 General purpose antioxidant-stabilizer. Also used in resins.                   TRADE NAME             SUPPLIER                                                __________________________________________________________________________     Antioxidant MO14       Aceto                                                   Ethyl Antioxidant 702  Ethyl                                                   Ethyl Antioxidant 728 (1)                                                                             Ethyl                                                   Lowinox 002            Lowi                                                    Prodox B-113           Ferro/Productol                                         __________________________________________________________________________      (1) `Soluble form`-                                                      

    4. Miscellaneous bisphenols - structures not revealed                                                SPECIFIC                                                 TRADE NAME    PHYS FORM                                                                              GRAVITY    SUPPLIER                                      __________________________________________________________________________     Cyanox 53 (1) White powder                                                                           1.74       Cyanamid                                      Naugawhite    Amber liquid                                                                           0.96       Uniroyal                                      Naugawhite Powder (1)                                                                        Tan powder                                                                             1.19       Uniroyal                                      Permanax WSO  White powder                                                                           1.00       Vulnax                                        Wytox PAP     Amber liquid                                                                           0.92       Olin                                          Wytox PSP-S (1)                                                                              Tan powder         Olin                                          Wytox PAP-SE (2)                                                                             Amber liquid                                                                           0.92       Olin                                          __________________________________________________________________________      (1) `On an inert carrier`-                                                     (2) Self emulsifiable form                                               

    5. 2,2'-Ethylidenebis(4,6-di-t-butylphenol)                                     ##STR13##                Mole Weight 438 White powder Melt Point                                        161-164° C. Specific Gravity 1.01             Antioxidant for rubber and plastics compounding.                               TRADE NAME             SUPPLIER                                                __________________________________________________________________________     Isonox 129             Schenectady                                             Vanox 1290             Vanderbilt                                              __________________________________________________________________________     6. 2,2'-Methylenebis(4-methyl-6-(1-methylcyclohexyl)phenol)                     ##STR14##                Mole Weight 422 Off-white powder Melt Point                                    120-130° C. Specific Gravity 1.17             Antioxidant for rubber and plastics compounding.                               TRADE NAME             SUPPLIER                                                __________________________________________________________________________     Nonox WSP              ICI                                                     Permanax WSP           Vulnax                                                  Permanax WSP (PQ)      Vulnax                                                  __________________________________________________________________________     7. 4,4'-Butylidinebis(6-t-butyl-m-cresol) or                                   4,4'-Butylidenebis(6-t-butyl-3-methylphenol)                                    ##STR15##                Mole Weight 382.5 White powder Melt Point                                      209° C. Specific Gravity 1.03                 Antioxidant for rubber, latex and plastics compounding.                        TRADE NAME             SUPPLIER                                                __________________________________________________________________________     Lowinox 44B25          Lowi                                                    Santowhite Powder      Monsanto                                                __________________________________________________________________________     8. Polybutylated Bisphenol A                                                                             Amber liquid                                                                   Specific Gravity 0.945-0.965                         Antioxidant for rubber compounding and raw polymer stabilization.              TRADE NAME             SUPPLIER                                                __________________________________________________________________________     Agerite Superlite      Vanderbilt                                              Agerite Superlite Solid (1)                                                                           Vanderbilt                                              Lowinox P22B           Lowi                                                    Vanox 1003             Vanderbilt                                              Vanox 1004 (Powder) (1)                                                                               Vanderbilt                                              __________________________________________________________________________      (1) 75% Agerite Superlite or Vanox 1003 and 25% inert carrier Specific         Gravity 1.26                                                             

    9. 4,4'-Thiobis(6-t-butyl-m-cresol) or                                         4,4'-Thiobis(6-t-butyl-3-metyhylphenol)                                         ##STR16##                Mole Weight 358.5 Light colored powder Melt                                    Point 150° C. Specific Gravity                                          1.06-1.12                                            Antioxidant for rubber, latex and plastics compounding. Widely used in         CR.                                                                            Activates CR cure systems.                                                     TRADE NAME             SUPPLIER                                                __________________________________________________________________________     Antioxidant TBM6 (1)   Aceto                                                   Lowinox 44S36          Lowi                                                    Santonox (2)           Monsanto                                                Santowhite Crystals    Monsanto                                                Santowhite MK (3)      Monsanto                                                __________________________________________________________________________      (1) Technical and pure grades                                                  (2) More pure form of Santowhite                                               (3) Reaction product grade                                               

    10. 4,4'-Methylenebis(2,6-dimethylphenol)                                       ##STR17##                Mole Weight 256                                      TRADE NAME             SUPPLIER                                                __________________________________________________________________________     Lowinox 44M26          Lowi                                                    __________________________________________________________________________     11. 1,1'-Thiobis(2-naphthol)                                                    ##STR18##                Mole Weight 318 Light yellow powder Melt Point                                 218° C. Min.                                  TRADE NAME             SUPPLIER                                                __________________________________________________________________________     SAO-30                 Southland                                               __________________________________________________________________________     12. Methylene bridged polyalkylphenol                                                                    Solid                                                                          Specific Gravity 1.02                                TRADE NAME             SUPPLIER                                                __________________________________________________________________________     Ethyl Antioxidant 738  Ethyl                                                   __________________________________________________________________________     13. 2,2'-Thiobis(4-methyl-6-t-butylphenol)                                      ##STR19##                Mole Weight 359                                      TRADE NAME PHYS FORM    MELT POINT                                                                               SUPPLIER                                     __________________________________________________________________________     SAO-4      Light yellow powder                                                                         70° C. Min.                                                                       Southland                                    SAO-6      White powder 83-86° C.                                                                         Southland                                    __________________________________________________________________________     14. Sulfur containing hindered phenol cyanurate                                                          White powder                                                                   Melt Point 190-194° C.                        TRADE NAME             SUPPLIER                                                __________________________________________________________________________     SAO-44                 Southland                                               __________________________________________________________________________     15. 2.2'-Isobutylidenebis(4,6-dimethylphenol)                                   ##STR20##                Mole Weight 298 White powder Specific Gravity                                  1.12                                                 TRADE NAME             SUPPLIER                                                __________________________________________________________________________     Lowinox 22IB46         Lowi                                                    Vulkanox NKF           Mobay                                                   __________________________________________________________________________     16. 2,2'-Methylenebis(4-methyl-6-cyclohexylphenol)                              ##STR21##                Mole Weight 393 Melt Point 125° C. Min.                                 Specific Gravity 1.08                                TRADE NAME             SUPPLIER                                                __________________________________________________________________________     Vulkanox ZKF           Mobay                                                   __________________________________________________________________________

    ______________________________________                                         POLYPHENOLS                                                                    ______________________________________                                         1. Butylated reaction product of p-cresol and dicyclopentadiene                 ##STR22##                                                                                     Average Mole Weight 600-700                                                    White powder or amber flake                                                    Melt Point 100° C.                                                      Specific Gravity 1.10                                          Non-staining antioxidant for general and high temperature                      applications. Especially recommended for NR, IR, SBR,                          CR and carboxylated polymers. Widely used in latex.                            TRADE NAME           SUPPLIER                                                  ______________________________________                                         WINGSTAY L Flake     GOODYEAR                                                  WINGSTAY L Powder    GOODYEAR                                                  ______________________________________                                         2. Tetrakis(methylene 3-(3,5-di-t-butyl-4-hydroxyphenyl)                       propionate) methane or Tetrakis(methylene (3,5-di-t-butyl-                     4-hydroxyhydrocinnamate) methane                                                ##STR23##                                                                                      Mole Weight 1178                                                              White crystalline powder                                                       Melt Point 110-125° C.                                                  Specific Gravity 1.45                                          TRADE NAME           SUPPLIER                                                  ______________________________________                                         Irganox 1010         CIBA-GEIGY                                                ______________________________________                                         3. 1,3,5-Trimethyl-2,4,6-tris(3,5-di-t-butyl-4-hydroxybenzyl)benzene            ##STR24##                                                                                     Mole Weight 775                                                                White crystalline powder                                                       Melt Point 244° C.                                      High performance antioxidant for plastics, rubber, resins                      and waxes.                                                                     TRADE NAME           SUPPLIER                                                  ______________________________________                                         Ethyl Antioxidant 330                                                                               Ethyl                                                     ______________________________________                                         4. 1,3,5-Tris(3,5-di-t-butyl-4-hydroxybenzyl)-s-triazine-2,4,6                 (1H,3H,5H)trione or 1,3,5-Tris(3,5-di-t-butyl-4-hydroxy-                       benzyl) isocyanurate                                                            ##STR25##                                                                                     White crystalline powder                                                       Melt Point 217-225° C.                                                  Specific Gravity 1.03                                          High temperature antioxidant recommended for plastics.                         TRADE NAME           SUPPLIER                                                  ______________________________________                                         Agerite GT           Vanderbilt                                                Good-rite 3114       Goodrich                                                  Vanox GT             Vanderbilt                                                ______________________________________                                         5. 3:1 Condensate of 3-methyl-6-t-butylphenol with crotonaldehyde                              White crystalline powder                                                       Melt Point 182.5-188° C.                                High performance antioxidant - recommended for plastics.                       TRADE NAME           SUPPLIER                                                  ______________________________________                                         Topanol CA           ICI                                                       ______________________________________                                         6. Phenolic condensation products with structures not revealed.                General purpose antioxidants for rubber and plastics                           compounding.                                                                                           SPECIFIC                                               TRADE NAME PHYS FORM    GRAVITY   SUPPLIER                                     ______________________________________                                         Akrochem   White powder 1.04      Akron                                        Antiox 33  (M P 100° C.    Chemical                                                Min.)                                                               Akrochem   White powder 1.05      Akron                                        Antiox 36  (M P 148° C.)   Chemical                                     Akrochem   White powder 1.04      Akron                                        Antiox 51  (M P 118° C.)   Chemical                                     Lowinox 22CP46                                                                            Powder                 Lowi                                         Mark 328   White powder           Argus                                        Nevastain A                                                                               Liquid       1.08-1.09 Neville                                      Nevastain B                                                                               Flake        1.09-1.11 Neville                                                 (M P 55° C.)                                                 Nevastain 76                                                                              Amber flake  1.1       Neville                                                 (M P 134° C.)                                                Stabilite 49-466                                                                          Powder (M P  1.04      Reichhold                                               110--110° C.)                                                Stabilite 49-467                                                                          Powder       1.05      Reichhold                                               (M P 148° C.)                                                Wytox PDA-S                                                                               Tan powder -           Olin                                                    contains inert                                                                 carrier                                                             Wytox PMW  Amber powder 1.05-1.07 Olin                                                    (M P 122° C.)                                                ______________________________________                                         7. 4-((4,6-Bis(octylthio)-2-triazin-2-yl)amino)-2,6-di-t-butylphenol or        2,4-(Bis(n-octylthio)-6-(4-hydroxy-3,5-di-t-butylanilino)1,3,5-triazine         ##STR26##                                                                                     White powder                                                                   Melt Point 93-98° C.                                    TRADE NAME           SUPPLIER                                                  ______________________________________                                         Irganox 565          CIBA-GEIGY                                                ______________________________________                                         Phenol/aldehyde condensates                                                    General purpose antioxidants.                                                                          SPECIFIC                                               TRADE NAME  PHYS FORM   GRAVITY   SUPPLIER                                     ______________________________________                                         Permanax EXP                                                                               Brown solid 1.07      Vulnax                                                   (M P 60° C.)                                                Permanax WMP (1)                                                                           Cream powder                                                                               1.54      Vulnax                                       ______________________________________                                          (1) Contains an inert carrier                                            

    ______________________________________                                         HYDROQUINONE DERIVATIVES                                                       ______________________________________                                         1. 2,5-Di-t-amylhydroquinone                                                    ##STR27##        Mole Weight 250 Off-white crystalline powder Melt Point                        179° C. Specific Gravity 1.02-1.05                    Polymer stabilizer and shortshop; also used in adhesives;                      slightly discoloring.                                                          TRADE NAME           SUPPLIER                                                  ______________________________________                                         Santovar A           Monsanto                                                  ______________________________________                                         2. t-Butylhydroquinone                                                          ##STR28##        Mole Weight 166 Off-white crystalline powder Melt Point                        127-129° C.                                           Polymer stabilizer and shortshop.                                              TRADE NAME           SUPPLIER                                                  ______________________________________                                         Tenox TBHQ           Eastman                                                   ______________________________________                                         3. Alkylated hydroquinone (structure not specified)                                            Viscous liquid (partially                                                      crystallizes)                                                                  Specific Gravity 0.90 @ 38° C.                          Antioxidant stabilizer for synthetic rubbers and plastics.                     TRADE NAME            SUPPLIER                                                 ______________________________________                                         Antioxidant 451      Uniroyal                                                  ______________________________________                                    

    ______________________________________                                         PHOSPHITES AND PHOSPHITE BLENDS                                                ______________________________________                                         1. Tris(nonylphenyl) phosphite                                                  ##STR29##           Amber, viscous liquid Specific Gravity 0.98               Non-staining stabilizer for raw polymer SBR and plastics.                      TRADE NAME           SUPPLIER                                                  ______________________________________                                         Interstab CH-55      Interstab                                                 Lowinox TNPP         Lowi                                                      Mark 1178            Argus                                                     Mark 1178B (1)       Argus                                                     Naugard P            Uniroyal                                                  Naugard PHR (1)      Uniroyal                                                  Polygard             Uniroyal                                                  Polygard HR (1)      Uniroyal                                                  Weston TNPP          Borg-Warner                                               Weston 399 (2)       Borg-Warner                                               Weston 399B (2)      Borg-Warner                                               Wytox 312            Olin                                                      Wytox 320            Olin                                                      ______________________________________                                          (1) Hydrolysis resistant grades                                                (2) More hydrolytically stable, containing TIPA                          

    2. Bis(2,4-di-t-butyl)pentaerythritol diphosphite                               ##STR30##                                                                                        Mole Weight 604                                                                White crystalline solid                                                        Melt Point 160-175° C.                               Antioxidant-stabilizer for rubbers and plastics.                               TRADE NAME           SUPPLIER                                                  ______________________________________                                         Weston MDW-626       Borg-Warner                                               ______________________________________                                         3. Distearyl pentaerythritol diphosphite                                        ##STR31##              Mole Weight 732 White flake Melt Point 40°                              C. Specific Gravity 0.94-0.96                          Antioxidant for plastics.                                                      TRADE NAME           SUPPLIER                                                  ______________________________________                                         Weston 618           Borg-Warner                                               Weston 619 (1)       Borg-Warner                                               ______________________________________                                          (1) More hydrolytically stable grade, containing TIPA                    

    4. `Polymeric` phosphites-structures not disclosed                             General purpose antioxidants and                                               stabilizers for rubber and plastics.                                                                  SPECIFIC                                                TRADE NAME PHYS FORM   GRAVITY    SUPPLIER                                     ______________________________________                                         Wytox 345  Yellow liquid                                                                              0.99       Olin                                         Wytox 345-S (1)                                                                           White powder           Olin                                         Wytox 438  Yellow liquid                                                                              1.01       Olin                                         Wytox 438-S (1)                                                                           Gray powder            Olin                                         Wytox 540  Liquid      1.003      Olin                                         Wytox 540-S (1)                                                                           Gray powder            Olin                                         ______________________________________                                          (1) Solid form on a carrier                                              

    5. Phosphited phenols and bisphenols-structures not revealed                   General purpose antioxidants for rubber and plastics.                                                 SPECIFIC                                                TRADE NAME PHYS FORM   GRAVITY    SUPPLIER                                     ______________________________________                                         Agerite Geltrol                                                                           Liquid      0.955-0.975                                                                               Vanderbilt                                   Naugard 492                                                                               Liquid      1.008      Uniroyal                                     Vanox 13   Liquid      0.93       Vanderbilt                                   Vanox 1005 Liquid      0.955-0.975                                                                               Vanderbilt                                   Vanox 1013 Liquid      0.93       Vanderbilt                                   Wytox 604  Liquid      0.89-0.93  Olin                                         Wytox 604-LMS                                                                             Liquid      0.948      Olin                                         Wytox 604-S (1)                                                                           Gray powder            Olin                                         ______________________________________                                          (1) Solid form                                                           

    ______________________________________                                         THIOESTERS                                                                     ______________________________________                                         6. Phosphite/phenolic antioxidant blends                                       TRADE NAME          SUPPLIER                                                   ______________________________________                                         Irganox B215 (1)    CIBA-GEIGY                                                 Irganox B225 (2)    CIBA-GEIGY                                                 Irganox B900 (3)    CIBA-GEIGY                                                 Irganox B1171 (4)   CIBA-GEIGY                                                 Weston 800 (5)      Borg-Warner                                                Weston 801 (6)      Borg-Warner                                                Weston 802 (7)      Borg-Warner                                                ______________________________________                                          Blends of tris(2,4-di-t-butylphenyl) phosphite and a phenolic antioxidant      as follows:                                                                    (1) 2:1 Blend with tetrakis(methylene(3,5di-t-butyl-4-hydroxy                  hydrocinnamate))methane(C2)                                                    (2) 1:1 Blend with tetrakis(methylene(3,5di-t-butyl-4-hydroxy                  hydrocinnamate))methane(C2)                                                    (3) 4:1 Blend with                                                             octadecyl(3,5di-t-butyl-4-hydroxybenzyl)phosphonate(G-1)                       (4) 1:1 Blend with 1,6hexamethylenebis-(3,5-di-t-butyl-4-hydroxy               hydrocinnamide)(G5)                                                            Blends of distearyl pentaerythritol diphosphite(E3) and tetrakis(methylen      3(3,5-di-t-butyl-4-hydroxyphenyl)propionate)methane as follows:                (5) 1:1 Blend                                                                  (6) 2:1 Blend                                                                  (7) 3:1 Blend                                                            

    1. Dilauryl thiodipropionate or Didodecyl 3,3'-thiodipropionate                 ##STR32##           Mole Weight 515 White waxy solid Melt Point                                    40-45° C. Specific Gravity 1.01                    Antioxidant for polyolefins and other plastics.                                TRADE NAME           SUPPLIER                                                  ______________________________________                                         Argus DLTDP          Argus                                                     Carstab DLTDP        Carstab                                                   Cyanox LTDP          Cyanamid                                                  Evanstab 12          Evans                                                     Lowinox DLTDP        Lowi                                                      Nonox DLTDP          ICI                                                       ______________________________________                                         2. Distearyl thiodipropionate or Dioctadecyl 3,3'-thiodipropionate              ##STR33##           Mole Weight 682 White waxy solid Melt Point                                    57-67° C. Specific Gravity 0.985                   Antioxidant for polyolefins and other plastics.                                TRADE NAME           SUPPLIER                                                  ______________________________________                                         Argus DSTDP          Argus                                                     Carstab DSTDP        Carstab                                                   Cyanox STDP          Cyanamid                                                  Evanstab 18          Evans                                                     Nonox DSTDP          ICI                                                       ______________________________________                                         3. Dimyristyl thiodipropionate                                                  ##STR34##           Mole Weight 571 White waxy solid Melt Point                                    44-48° C.                                          Antioxidant for polyolefins and other plastics.                                TRADE NAME           SUPPLIER                                                  ______________________________________                                         Argus DMTDP          Argus                                                     Carstab DMTDP        Carstab                                                   CYanox MTDP          Cyanamid                                                  Evanstab 14          Evans                                                     ______________________________________                                         4. Ditridecyl thiodipropionate                                                  ##STR35##           Mole Weight 543 Colorless liquid Specific Gravity                              0.936                                                     TRADE NAME           SUPPLIER                                                  ______________________________________                                         Argus DTDTDP         Argus                                                     Cyanox 711           Cyanamid                                                  Evanstab 13          Evans                                                     ______________________________________                                         5. Mixed esters(lauryl and stearyl) of thiodipropionic acid                     ##STR36##      Mole Weight 599 White crystalline powder or flakes Melt                        Point 50° C.                                            TRADE NAME           SUPPLIER                                                  ______________________________________                                         Cyanox 1212          Cyanamid                                                  ______________________________________                                         6. Pentaerythritol tetrakis(3-(dodecylthio)propionate)                          ##STR37##             Mole Weight 1162 White solid Melt Point 50°                             C. Min.                                                 Antioxidant for polyolefins and other plastics.                                TRADE NAME           SUPPLIER                                                  ______________________________________                                         Seenox 412-S         Argus                                                     ______________________________________                                         7. Blend of a phenolic and thioester type antioxidant.                                         White powder                                                                   Specific Gravity 1.04, 1.76 (1)                                Antioxidant systems for polyolefins.                                           TRADE NAME           SUPPLIER                                                  ______________________________________                                         Vanox 1030           Vanderbilt                                                Vanox 1040 (1)       Vanderbilt                                                ______________________________________                                          (1) Contains a mineral deactivator for mineral filled compounds.         

    __________________________________________________________________________     MULTIFUNCTIONAL NON-STAINING ANTIOXIDANTS                                      __________________________________________________________________________     1. O,ODi-n-octadecyl(3,5-di-t-butyl-4-hydroxybenzyl)phosphonate                 ##STR38##                                   Mole Weight 805 White                                                          crystalline powder Melt                                                        Point 45° C. Min.                                                       Specific Gravity 0.96             Antioxidant, stabilizer for plastics.                                          TRADE NAME                                   SUPPLIER                          __________________________________________________________________________     Irganox 1093                                 CIBA-GEIGY                        __________________________________________________________________________     2. 1,6-Hexamethylene bis(3,5-di-t-butyl-4-hydroxyhydrocinnamate)               1,6-Hexamethylene bis(3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate)             ##STR39##                                   Mole Weight 639 Off-white                                                      crystalline powder Melt                                                        Point 94-108° C.           General purpose antioxidant for plastics and elastomers.                       TRADE NAME                                   SUPPLIER                          __________________________________________________________________________     Irganox 259                                  CIBA-GEIGY                        __________________________________________________________________________     3. Thiodiethylene bis(3,5-di-t-butyl-4-hydroxy)hydrocinnamate or               Thiodiethylene bis(3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate)                ##STR40##                                   Mole Weight 642 White                                                          crystalline powder Melt                                                        Point 63° C. Min.                                                       Specific Gravity 1.19             Antioxidant for plastic and elastomers.                                        TRADE NAME                                   SUPPLIER                          __________________________________________________________________________     Irganox 1035                                 CIBA-GEIGY                        __________________________________________________________________________     4. Octadecyl 3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate or                   Octadecyl 3,5-di-t-butyl-4-hydroxyhydrocinnamate                                ##STR41##                                   Mole Weight 531 White                                                          crystalline powder Specific                                                    Gravity 1.02 Melt Point                                                        49-54° C.                  Antioxidants for plastics and elastomers.                                      TRADE NAME                                   SUPPLIER                          __________________________________________________________________________     Irganox 1076                                 CIBA-GEIGY                        __________________________________________________________________________     5. N,N'Hexamethylene bis(3,5-di-t-butyl-4-hydroxyhydrocinnamamide) or           N,N'Hexamethylene bis(3-(3,5-di-t-butyl-4-hydroxyphenyl)propionamide)          ##STR42##                                   Mole Weight 637 White                                                          crystalline powder Specific                                                    Gravity 1.05 Melt Point                                                        156-162° C.                Antioxidants for polyamides, plastics and elastomers.                          TRADE NAME                                   SUPPLIER                          __________________________________________________________________________     Irganox 1098                                 CIBA-GEIGY                        __________________________________________________________________________     6. 3,5-Di-t-butyl-4-hydroxyhydrocinnamic acid triester with                    1,3,5-Tris(2-hydroxyethyl)-s-triazine-2,4,6-(1H,3H,5H)trione                    ##STR43##                                                                                                            ##STR44##                                                                            Mole Weight 1042                                                               White crystalline powder                                                       Specific Gravity 0.921                                                         Melt Point 123-131°                                                     C.                                Antioxidant for plastics.                                                      TRADE NAME                                   SUPPLIER                          __________________________________________________________________________     Good-rite 3125                               Goodrich                          Agerite SKT, Vanox SKT                       Vanderbilt                        __________________________________________________________________________     7. NButyryl-p-aminophenol or N(4-Hydroxyphenyl)butyramide                       ##STR45##                                   Mole Weight 179 White powder                                                   elt Point 136-141°                                                      C.                                Antioxidants for plastics and elastomers.                                      TRADE NAME                                   SUPPLIER                          __________________________________________________________________________     Suconox 4                                    Hexel                             __________________________________________________________________________     8. NPelargonoyl-p-aminophenol or N(4-Hydroxyphenyl)pelargonamide                ##STR46##                                   Mole Weight 249 White powder                                                   elt Point 121-125°                                                      C.                                Antioxidant for plastics and elastomers.                                       TRADE NAME                                   SUPPLIER                          __________________________________________________________________________     Suconox 9                                    Hexel                             __________________________________________________________________________     9. NLauroyl-p-aminophenol or N(4-Hydroxyphenyl)dodecanamide                     ##STR47##                                   Mole Weight 291 White powder                                                    Melt Point 130-134°                                                    C.                                Antioxidant for plastics, butyl rubber and elastomers.                         TRADE NAME                                   SUPPLIER                          __________________________________________________________________________     Suconox 12                                   Hexel                             __________________________________________________________________________     10. NStearoyl-p-aminophenol or N(4-Hydroxyphenyl)stearamide                     ##STR48##                                   Mole Weight 376 White powder                                                   elt Point 130-134°                                                      C.                                Antioxidant for polyethylene and polyamides.                                   TRADE NAME                                   SUPPLIER                          __________________________________________________________________________     Suconox 18                                   Hexel                             __________________________________________________________________________     11. 2,6-Di-t-butyl-alpha-dimethylamino-p-cresol or                             2,6-Di-t-butyl-4-(dimethylaminomethyl)phenol                                    ##STR49##                                   Mole Weight 263 Light yellow                                                   crystalline powder Melt                                                        Point 94° C.               Antioxidant for plastics and elastomers.                                       TRADE NAME                                   SUPPLIER                          __________________________________________________________________________     Ethyl Antioxidant 703                        Ethyl                             __________________________________________________________________________     12. 1,3,5-Tris(4-t-butyl-3-hydroxy-2,6-dimethylbenzyl)-s-triazine-2,4,6-(1     H,3H,5H)trione                                                                  ##STR50##                                                                                                                   ##STR51##                                                                     Mole Weight 699                                                                Off-white powder                                                               Melt Point 145-155°                                                     C.                                TRADE NAME                                   SUPPLIER                          __________________________________________________________________________     Cyanox 1790                                  Cyanamid                          __________________________________________________________________________     13. Nickel bis(Oethyl(3,5-di-t-butyl-4-hydroxybenzyl)phosphonate)               ##STR52##                                   Mole Weight 714 Tan-light                                                      green powder Melt Point                                                        180° C. Min.               Antioxidant/UV absorber for plastics.                                          TRADE NAME                                   SUPPLIER                          __________________________________________________________________________     Irgastab 2002                                CIBA-GEIGY                        __________________________________________________________________________     14. 2,2'-Oxamidobisethyl 3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate           ##STR53##                                   Mole Weight 697 Off-white                                                      powder Melt Point                                                              173° C.                    Antioxidant and metal deactivator.                                             TRADE NAME                                   SUPPLIER                          __________________________________________________________________________     Naugard XL-1                                 Uniroyal                          __________________________________________________________________________     15. Phenolic antioxidant/metal deactivator - undisclosed composition.                   SPECIFIC                                                              TRADE NAME                                                                              GRAVITY               MELT POINT                                                                             SUPPLIER                                __________________________________________________________________________     Irganox MD-1024                                                                         1.12                  224° C. Min.                                                                    CIBA-GEIGY                              __________________________________________________________________________     16. Tris(2-t-butyl-4-(2-methyl-4-hydroxy-5-t-butylphenylthio)-5-methyl)phe     nylphosphite                                                                    ##STR54##                                   Mole Weight 1103                  Antioxidant and metal deactivator                                                                                SPECIFIC                                     TRADE NAME PHYS FORM              GRAVITY                                                                              SUPPLIER                               __________________________________________________________________________     Antioxidant VP OSP 1                                                                      White powder           1.10  Hoechst                                __________________________________________________________________________     17. Bis(3,3-bis(4-hydroxy-3-t-butylphenyl)butanoic acid)glycolester                                                         Mole Weight 795                                                                Melt Point 170° C.                                          SPECIFIC                                      TRADE NAME                                                                              PHYS FORM               GRAVITY                                                                              SUPPLIER                                __________________________________________________________________________     Hostanox 03                                                                             White powder            1.1   Hoechst                                 __________________________________________________________________________     18. Tetrakis(2,4-di-t-butylphenyl)4,4'-biphenylylenediphosphonite               ##STR55##                                   Mole Weight 1035                                                   SPECIFIC                                      TRADE NAME                                                                              PHYS FORM               GRAVITY                                                                              SUPPLIER                                __________________________________________________________________________     Sandostab P-EPQ                                                                         75° C.           1.045 Sandoz                                  __________________________________________________________________________     19. n-Propyl gallate or n-Propyl 3,4,5-tri-hydroxybenzoate                      ##STR56##                                   Mole Weight 212  White                                                         powder Melt Point                                                              146-148° C.                TRADE NAME                                   SUPPLIER                          __________________________________________________________________________     Tenox PG                                     Eastman                           __________________________________________________________________________     20. Calcium bis(Oethyl(3,5-di-t-butyl-4-hydroxybenzyl)phosphonate)              ##STR57##                                   Mole Weight 647 Off-white                                                      powder Melt Point                                                              >260° C.                   Antioxidant/metal deactivator                                                  TRADE NAME                                   SUPPLIER                          __________________________________________________________________________     Irganox 1425                                 CIBA-GEIGY                        __________________________________________________________________________     21. Phenolic Antioxidant - composition undisclosed.                            Antioxidant/metal deactivator.                                                 TRADE NAME            PHYSICAL FORM                                                                            SUPPLIER                                       __________________________________________________________________________     Lowinox 22CP46-MD     Off-white powder                                                                         Lowi                                           __________________________________________________________________________

    ______________________________________                                         MISCELLANEOUS UNCLASSIFIED                                                     NON-STAINING ANTIOXIDANTS AND BLENDS                                           ______________________________________                                         1. 1.2-Mercapto-4(5)-methylbenzimidazole                                        ##STR58##          Mole Weight 164 Yellow-white powder Specific Gravity                           1.25 Melt Point 270° C.                             and                                                                             ##STR59##                                                                     Antioxidant, synergist and metal deactivator.                                  TRADE NAME          SUPPLIER                                                   ______________________________________                                         Vulkanox MB-2/MG    Mobay                                                      ______________________________________                                         2. Zinc salt of 2-mercaptobenzimidazole                                         ##STR60##          White powder Specific Gravity 1.75 Melt Point >                                300° C. with decomposition.                         Antioxidant and synergist.                                                     TRADE NAME          SUPPLIER                                                   ______________________________________                                         Akrochem Antioxidant 58                                                                            Akron Chemical                                             Naugard ZMB         Uniroyal                                                   ______________________________________                                         3. 2-Mercapto-4-methylbenzimidazole, zinc salt,                                2-Mercapto-5-methylbenzimidazole, zinc salt                                     ##STR61##                                                                                 SPECIFIC                                                           TRADE NAME  GRAVITY   MELT POINT  SUPPLIER                                     ______________________________________                                         Vulkanox ZMB-2/C                                                                           1.75      >300° C.                                                                            Mobay                                        ______________________________________                                         4. Antioxidants of undisclosed composition, including blends.                  TRADE NAME     PHYS FORM     SUPPLIER                                          ______________________________________                                         Mark 1220      Yellow liquid Argus                                             Mark 1475 (1)  White powder  Argus                                             Mark 2112      White powder  Argus                                             Mark 2183 (1)  Tan powder    Argus                                             ______________________________________                                          (1) Antioxidant/chelator.  -                                             

    5. Phosphite/phenolic antioxidant blends                                                               SPECIFIC                                               TRADE NAME  PHYS FORM   GRAVITY   SUPPLIER                                     ______________________________________                                         Mark 1409   Liquid      0.99      Argus                                        Mark 1409-S (1)                                                                            Granules    1.18      Argus                                        ______________________________________                                          (1) Solid form of Mark 1409  -                                           

    6. Thioester/phenolic antioxidant blends                                       General purpose antioxidants used mainly in plastics.                                                 SPECIFIC                                                TRADE NAME PHYS FORM   GRAVITY    SUPPLIER                                     ______________________________________                                         Mark 158   Yellow liquid                                                                              0.982      Argus                                        Mark 1589  White powder                                                                               1.17       Argus                                        Mark 1589B White powder                                                                               1.17       Argus                                        ______________________________________                                         7. 2-Mercaptotoluimidazole                                                      ##STR62##          Mole Weight 164 Melt Point 250° C. Min.             Non-staining antioxidant and synergist.                                                               SPECIFIC                                                TRADE NAME PHYS FORM   GRAVITY    SUPPLIER                                     ______________________________________                                         Vanox MTI  Tan powder  1.33       Vanderbilt                                   ______________________________________                                         8. Zinc 2-mercaptotoluimidazole                                                 ##STR63##           Mole Weight 391                                           Non-staining antioxidant and synergist.                                                               SPECIFIC                                                TRADE NAME PHYS FORM   GRAVITY    SUPPLIER                                     ______________________________________                                         Vanox ZMTI Tan powder  1.69       Vanderbilt                                              Melt Point >                                                                   300° C.                                                      ______________________________________                                         9. Dioctadecyl disulfide                                                        H.sub.38 C.sub.18SSC.sub.18 H.sub.38                                                             Mole Weight 571                                                                Melt Point 53-58° C.                                                         SPECIFIC                                               TRADE NAME  PHYS FORM   GRAVITY   SUPPLIER                                     ______________________________________                                         Antioxidant SE10                                                                           White powder                                                                               0.85@55° C.                                                                       Hoechst                                      ______________________________________                                         10. Blends including a phenolic antioxidant-undisclosed composition.                       SPECIFIC    MELT                                                   TRADE NAME  GRAVITY     POINT     SUPPLIER                                     ______________________________________                                         Antioxidant AO-19                                                                          1.03        110-200° C.                                                                       Sovereign                                    Antioxidant 35                                                                             1.04        105-115° C.                                                                       Sovereign                                    Powder                                                                         Antioxidant 872                                                                            1.03        122° C.                                                                           Sovereign                                    ______________________________________                                         11. Blend of non-staining antioxidants                                                                 SPECIFIC                                               TRADE NAME  PHYS FORM   GRAVITY   SUPPLIER                                     ______________________________________                                         Permanax CNS                                                                               Cream powder                                                                               1.25      Vulnaz                                                   Melt Point                                                                     298° C.                                                     ______________________________________                                         12. Metal aromatic sulfonate                                                   Mineral deactivator.                                                                                   SPECIFIC                                               TRADE NAME  PHYS FORM   GRAVITY   SUPPLIER                                     ______________________________________                                         Vanox 3240  Brown liquid                                                                               0.98      Vanderbilt                                   Vanox 3245  Brown flake 1.12      Vanderbilt                                   ______________________________________                                    

    ______________________________________                                         NAPHTHYLAMINES                                                                 ______________________________________                                         1. NPhenyl-alpha-naphthylamine                                                  ##STR64##         Mole Weight 219 Tan-purple powder Melt point                                   50-59° C. Specific Gravity 1.16-1.20                 TRADE NAME         SUPPLIER                                                    ______________________________________                                         Additin 30         Mobay                                                       Akrochem Antioxidant PANA                                                                         Akron Chemical                                              Naugard PAN        Uniroyal                                                    ______________________________________                                         2. NPhenyl-beta-naphthylamine (Commonly called `PBNA`)                          ##STR65##         Mole Weight 219 Dark Solid Melt Point 105-106°                          C. Specific Gravity 1.18-1.24                               Powerful staining antioxidant exstensively used in Europe.                     No known suppliers in the USA.                                                 ______________________________________                                    

    __________________________________________________________________________     DIPHENYLAMINE AND OTHER DIARYLAMINE DERIVATIVES                                __________________________________________________________________________     1. p-Oriented styrenated diphenylamine                                          ##STR66##                                                                     Mostly di substituted with some mono and tri substituted species.              Some ortho substitution.                                                       Highly active non-staining, mildly discoloring amine for natural and           synthetic                                                                      polymers and compounds.                                                               TRADE NAME          SUPPLIER                                            __________________________________________________________________________            WINGSTAY 29         GOODYEAR                                                   WINGSTAY 29 Powder (1)                                                                             GOODYEAR                                                   Lowinox SDA (2)     Lowi                                                       Vulkanox DDA (2)    Mobay                                               __________________________________________________________________________      (1) Solid form of WINGSTAY 29  70% active  Specific Gravity 1.53               (2) Orientation and amount of styrenation not listed.                    

    2. Octylated diphenylamines                                                     ##STR67##                                                                     General purpose semi-staining antioxidants for polymers and compounds                                     SPECIFIC                                            TRADE NAME                                                                               PHYS FORM                                                                               MELT POINT                                                                             GRAVITY                                                                              SUPPLIER                                      __________________________________________________________________________     Agerite Gel (1)                                                                          Tan waxy solid                                                                          40-50° C.                                                                       0.94  Vanderbilt                                    Agerite Stalite S                                                                        Tan powder                                                                              89-103° C.                                                                      1.02  Vanderbilt                                    Akrochem Antiox S                                                                        Brown granules                                                                          88° C. Min.                                                                     1.00  Akron                                                                          Chemical                                      Cyanox 8  Gray flakes                                                                             75-85° C.                                                                       0.98  Cyanamid                                      Flectol ODP                                                                              Tan powder                                                                              89-103° C.                                                                      0.99  Monsanto                                      Octamine  Tan solid                                                                               85° C. Min.                                                                     0.99  Uniroyal                                      Pennox ODP                                                                               Tan powder                                                                              88-98° C.                                                                       1.02  Pennwalt                                      Permanax OD                                                                              Tan granules                                                                            90° C.                                                                          1.12  Vulnax                                        Vanox 12  Tan granules                                                                            94-100° C.                                                                      1.01  Vanderbilt                                    Vanox 1081                                                                               Tan granules                                                                            94-100° C.                                                                      1.02  Vanderbilt                                    Vulkanox OCD                                                                             Tan granules                                                                            90° C.                                                                          1.12  Mobay                                         __________________________________________________________________________      (1) Contains 25% wax                                                     

    3. Other alkylated diphenylamines                                               ##STR68##                                                                     General purpose semi-staining antioxidants.                                                             SPECIFIC                                              TRADE NAME     PHYS FORM GRAVITY SUPPLIER                                      __________________________________________________________________________     Agerite NEPA (1)                                                                              Amber liquid                                                                             0.935   Vanderbilt                                    Agerite Stalite (2)                                                                           Dark liquid                                                                              1.01    Vanderbilt                                    Pennox A (2)   Dark liquid                                                                              0.995-1.025                                                                            Pennwalt                                      Permanax HD (3)                                                                               Brown liquid                                                                             0.97    Vulnax                                        Permanax HD(SE) (4)                                                                           Brown liquid                                                                             0.97    Vulnax                                        Polylite (5)   Dark liquid                                                                              0.95    Uniroyal                                      Vanox 1001 (1) Amber liquid                                                                             0.935   Vanderbilt                                    Wytox ADP-F (1)                                                                               Gray flake                                                                               0.99    Olin                                          __________________________________________________________________________      (1) Alkylation not specified                                                   (2) Octylated                                                                  (3) Heptylated                                                                 (4) Self emulsifying form                                                      (5) Nonylated                                                            

    4. High temperature reaction products of diphenylamine and acetone             Powerful amine antioxidants for rubber compounds used frequently to            impart high temperature resistance. Rather severe staining                                              SPECIFIC                                              TRADE NAME     PHYS FORM GRAVITY SUPPLIER                                      __________________________________________________________________________     Agerite Superflex (1)                                                                         Dark liquid                                                                              1.10    Vanderbilt                                    Agerite Superflex                                                                             Dk br powder                                                                             1.33    Vanderbilt                                    Solid G (3)                                                                    Agerite Superflex                                                                             Dk brown rods                                                                            1.34    Vanderbilt                                    Solid Rodform (2)                                                              BLE-25         Dark br liquid                                                                           1.10    Uniroyal                                      BLE-75         Dk br powder                                                                             1.33    Uniroyal                                      Permanax BL    Brown liquid                                                                             1.09-1.10                                                                              Vulnax                                        Permanax BLN   Brown liquid                                                                             1.09-1.10                                                                              Vulnax                                        Permanax BLW (5)                                                                              Brown solid                                                                              1.26    Vulnax                                        __________________________________________________________________________      (1) Contains 20% diphenylamine                                                 (2) 32.5% Inert carrier                                                        (3) 15% Diphenylamine, 25% inert carrier                                       (4) 75% Active on microcel                                                     (5) Contains a silicate carrier                                          

    5. Low temperature reaction product of diphenylamine and acetone                                             Brown-green powder                                                             Specific Gravity 1.15                            General purpose antioxidant.                                                   TRADE NAME   MELT POINT       SUPPLIER                                         __________________________________________________________________________     Aminox       85-95° C. Uniroyal                                         Permanax B   75-90° C. Vulnax                                           __________________________________________________________________________     6. Diarylamine/ketone/aldehyde reaction products                                                         Dark brown solids                                                              Melt Point 85-95° C.                                                    Specific Gravity 1.15                                General purpose antioxidants.                                                          TRADE NAME        SUPPLIER                                             __________________________________________________________________________             BXA-G             Uniroyal                                                     Naugard BG        Uniroyal                                                     Vanox AT          Vanderbilt                                           __________________________________________________________________________     7. Substituted diphenylamine-structure not revealed                                                      Off-white powder                                                               Melt point 96-99° C.                                                    Specific Gravity 1.14                                Non-discoloring amine antioxidant for polymers and plastics.                           TRADE NAME        SUPPLIER                                             __________________________________________________________________________             Naugard 445       Uniroyal                                             __________________________________________________________________________

    __________________________________________________________________________     p-PHENYLENEDIAMINES                                                            __________________________________________________________________________     1. NPhenyl-N'(1,3-dimethylbutyl)p-phenylenediamine                              ##STR69##                                                                     Powerful and persistent antioxidant, flex crack inhibitor and                  antiozonant.                                                                   TRADE NAME                 SUPPLIER                                            __________________________________________________________________________     WINGSTAY 300               GOODYEAR                                            Akrochem Antiozonant PD #2 Akron Chem                                          Anto 3E                    Pennwalt                                            Antozite 67                Vanderbilt                                          Antozite 67F (1)           Vanderbilt                                          Flexzone 7F, (1)           Uniroyal                                            Flexzone 7L                Uniroyal                                            Permanax 6PPD              Vulnax                                              Santoflex 13               Monsanto                                            Santoflex 13F, (1)         Monsanto                                            UOP 588                    UOP                                                 Vulkanox 4020              Mobay                                               Vulkanox 4020 Flake (1)    Mobay                                               __________________________________________________________________________      (1) Flaked form                                                          

    2. NPhenyl-N'isopropyl-p-phenylenediamine                                       ##STR70##                                                                     Powerful antioxidant-antiozonant.                                              TRADE NAME                  SUPPLIER                                           __________________________________________________________________________     Akrochem Antiozonant PD #1  Akron Chem                                         Anto 3H                     Pennwalt                                           Flexzone 3C                 Uniroyal                                           Permanax IPPD               Vulnax                                             Santoflex IP                Monsanto                                           Vulkanox 4010NA             Mobay                                              __________________________________________________________________________     3. NPhenyl-N'(1-methylheptyl)-p-phenylenediamine                                ##STR71##                                                                     Antioxidant-antiozonant.                                                               TRADE NAME        SUPPLIER                                             __________________________________________________________________________             UOP 688           UOP                                                  __________________________________________________________________________     4. NPhenyl-N'cyclohexyl-p-phenylenediamine                                      ##STR72##                                                                     Antioxidant-antiozonant.                                                               TRADE NAME        SUPPLIER                                             __________________________________________________________________________             Flexzone 6H       Uniroyal                                             __________________________________________________________________________     5. Mixed diaryl-p-phenylenediamines                                             ##STR73##                                                                     Persistent antioxidants, antiozonants and antiflex agents for many             natural and synthetic                                                          rubber compounds. Very powerful antiozonants for CR. Very non-volatile         and slow to                                                                    extract.                                                                                  PHYSICAL MELT  SPECIFIC                                             TRADE NAME FORM     POINT GRAVITY                                                                               SUPPLIER                                      __________________________________________________________________________     WINGSTAY 100                                                                              Silver-gray flakes                                                                      90-105° C.                                                                    1.18   GOODYEAR                                      WINGSTAY 100AZ                                                                            Gray flakes                                                                             110° C.                                                                       1.18   GOODYEAR                                      (1)                                                                            WINGSTAY 200                                                                              Low-melting                                                                             60° C.                                                                        1.18   GOODYEAR                                                 semi-solid                                                          __________________________________________________________________________      (1) Special low scorch grade for neoprene (CR)                                6. N,N'Diphenyl-p-phenylenediamine                                              ##STR74##                                                                     General purpose antioxidant and flex crack inhibitor. Limited solubility       in most polymers.                                                                      TRADE NAME        SUPPLIER                                             __________________________________________________________________________             Agerite DPPD      Vanderbilt                                                   J-Z-F             Uniroyal                                                     Naugard J         Uniroyal                                                     Permanax DPPD     Vulnax                                               __________________________________________________________________________     7. N,N'Di-beta-naphthyl-p-phenylenediamine                                      ##STR75##                                                                     Antioxidant and metal deactivator. Not an antiozonant.                                TRADE NAME          SUPPLIER                                            __________________________________________________________________________            Agerite White       Vanderbilt                                                 Agerite White White (1)                                                                            Vanderbilt                                          __________________________________________________________________________      (1) Special grade                                                        

    8. N,N'Bis(1,4-dimethylpentyl)-p-phenylenediamine                               ##STR76##                                                                     General purpose antiozonant. Activates cure systems.                                   TRADE NAME        SUPPLIER                                             __________________________________________________________________________             Flexzone 4L       Uniroyal                                                     Santoflex 77      Monsanto                                                     UOP 788           UOP                                                  __________________________________________________________________________     9. N,N'Bis(1-ethyl-3-methylpentyl)-p-phenylenediamine                           ##STR77##                                                                     General purpose antiozonant. Activates cure systems.                                   TRADE NAME        SUPPLIER                                             __________________________________________________________________________             Antozite 2        Vanderbilt                                                   Flexzone 8L       Uniroyal                                                     UOP 88            UOP                                                  __________________________________________________________________________     10. N,N'Bis(1-methylheptyl)-p-phenylenediamine                                  ##STR78##                                                                     General purpose antiozonant. Activates cure systems.                                   TRADE NAME        SUPPLIER                                             __________________________________________________________________________             Antozite 1        Vanderbilt                                                   Santoflex 217     Monsanto                                                     UOP 288           UOP                                                  __________________________________________________________________________     11. NPhenyl-N'-(p-toluenesulfonyl)-p-phenylenediamine                           ##STR79##                                                                     Semi-discoloring antioxidant and copper inhibitor.                                     TRADE NAME        SUPPLIER                                             __________________________________________________________________________             Aranox            Uniroyal                                             __________________________________________________________________________

    ______________________________________                                         QUINOLINES                                                                     ______________________________________                                         1. Polymerized 2,2,4-trimethyl-1,2-dihydroquinoline                             ##STR80##                                                                     General purpose semi-staining antioxidant used in dry rubber and               latex compounding. Used to impart high temperature resistance.                 Functions As a mild antiozonant. Specific Gravity 1.04-1.08                                            MELT                                                   TRADE NAME  PHYS FORM   POINT     SUPPLIER                                     ______________________________________                                         Agerite MA  Tan powder  74° C. Min.                                                                       Vanderbilt                                   Agerite ME Pellets                                                                         Tan pellets 74° C. Min.                                                                       Vanderbilt                                   Agerite PE Pellets                                                                         Amber pellets                                                                              88° C. Min.                                                                       Vanderbilt                                   Agerite Resin D                                                                            Amber pellets                                                                              74° C. Min.                                                                       Vanderbilt                                   Agerite Resin D                                                                            Amber powder                                                                               74° C. Min.                                                                       Vanderbilt                                   Powder                                                                         Akrochem    Amber powder                                                                               75° C. Min.                                                                       Akron                                        Antioxidant DQ                    Chemical                                     Cyanox 12   Tan powder  75-110° C.                                                                        Cyanamid                                                 or flakes                                                          Flectol H   Tan powder  75-110° C.                                                                        Monsanto                                     Lowinox ACP                       Lowi                                         Naugard Q   Amber powder                                                                               75° C. Min.                                                                       Uniroyal                                     Pennox HR Flake                                                                            Tan flake   75-110° C.                                                                        Pennwalt                                     Pennox HR Powder                                                                           Tan powder  75-110° C.                                                                        Pennwalt                                     Permanax TQ Brown flake 79° C. Min.                                                                       Vulnax                                       Vulkanox HS Amber pellets                                                                              75° C.                                                                            Mobay                                        ______________________________________                                         2. 6-Dodecyl-2,2,4-trimethyl-1,2-dihydroquinoline                               ##STR81##                                                                     General purpose antioxidant.                                                                           SPECIFIC                                               TRADE NAME  PHYS FORM   GRAVITY   SUPPLIER                                     ______________________________________                                         Santoflex DD                                                                               Dark liquid 0.90-0.96 Monsanto                                     ______________________________________                                         3. 6-Ethoxy-2,2,4-trimethyl-1,2-dihydroquinoline                                ##STR82##                                                                     Highly staining antioxidant and antiozonant.                                                           SPECIFIC                                               TRADE NAME  PHYS FORM   GRAVITY   SUPPLIER                                     ______________________________________                                         Santoflex AW                                                                               Dark liquid 1.02-1.05 Monsanto                                     Vulkanox EC Dark liquid 1.02-1.05 Mobay                                        ______________________________________                                    

    ______________________________________                                         BLENDED AMINES                                                                 ______________________________________                                         1. 65% Dioctylated diphenylamine (J-2) and 35% N,N'--diphenyl-                 p-phenylenediamine (K-6)                                                       Antioxidant and flex cracking inhibitor.                                                         Melt Point 80-100° C.                                                         SPECIFIC                                               TRADE NAME  PHYS FORM   GRAVITY   SUPPLIER                                     ______________________________________                                         Agerite HP-S                                                                               Black powder                                                                               1.11      Vanderbilt                                   Agerite HP-S                                                                               Black Rodform                                                                              1.11      Vanderbilt                                   Rodform                                                                        ______________________________________                                         2. 50% Octylated diphenylamine (J-2), 25% N,N'--diphenyl-p-                    phenylenediamine (K-6) and 25% high temperature reaction product               of diphenylamine and acetone. (J-4)                                            Antioxidant and flex cracking inhibitor.                                                         Melt Point 70° C. Min.                                                        SPECIFIC                                               TRADE NAME  PHYS FORM   GRAVITY   SUPPLIER                                     ______________________________________                                         Agerite Hipar T                                                                            Brown powder                                                                               1.15      Vanderbilt                                   ______________________________________                                         3. 65% Diarylamine/ketone reaction product and                                 35% N,N'--diphenyl-p-phenylenediamine (K-6)                                    Antioxidant, flex cracking inhibitor and metal deactivator.                                      Melt Point 87-99° C.                                                          SPECIFIC                                               TRADE NAME  PHYS FORM   GRAVITY   SUPPLIER                                     ______________________________________                                         Flexamine   Brown powder                                                                               1.17      Uniroyal                                     Flexamine G Brown granules                                                                             1.17      Uniroyal                                     ______________________________________                                         4. p-Phenylenediamine antiozonant blends-undisclosed composition.              TRADE NAME     PHYS FORM    SUPPLIER                                           ______________________________________                                         Flexzone 10L   Dark liquid  Uniroyal                                           Flexzone 11L   Dark liquid  Uniroyal                                           Flexzone 12L   Dark liquid  Uniroyal                                           Flexzone 15L   Dark liquid  Uniroyal                                           Santoflex 134  Dark liquid  Monsanto                                           UOP 57 (1)     Dark liquid  UOP                                                UOP 62 (2)     Dark liquid  UOP                                                UOP 256 (3)    Dark liquid  UOP                                                ______________________________________                                          (1) Blend of UOP 588 and UOP 788                                               (2) Blend of UOP 288 and UOP 688                                               (3) Blend of UOP 288, UOP 588 and UOP 688                                

    5. Blend of 50% N,N'--bis(1,4-dimethylpentyl)-p-phenylenediamine               (K-8) and 50% N--phenyl-N'--(1,3-dimethylbutyl)-p-                             phenylenediamine (K-1)                                                         General purpose antiozonant blend.                                             TRADE NAME     PHYS FORM    SUPPLIER                                           ______________________________________                                         Flexzone 9L    Dark liquid  Uniroyal                                           ______________________________________                                         6. Antidegradant blends-undisclosed composition.                               General purpose antidegradant which may or may not be                          an antiozonant.                                                                                        SPECIFIC                                               TRADE NAME  PHYS FORM   GRAVITY   SUPPLIER                                     ______________________________________                                         Naugard 477 Brown powder                                                                               1.18      Uniroyal                                     Permanax CR Brown granules                                                                             1.14      Vulnax                                       ______________________________________                                         7. Antidegradant blends                                                        General purpose antidegradants.                                                                        SPECIFIC                                               TRADE NAME  PHYS FORM   GRAVITY   SUPPLIER                                     ______________________________________                                         Santoflex LC (1)                                                                           Dark liquid 1.023     Monsanto                                     Santoflex 134D (2)                                                                         Dark liquid 0.96      Monsanto                                     Santoflex 715 (3)                                                                          Dark liquid 0.98      Monsanto                                     ______________________________________                                          (1) 1 Part N--(1,3dimethylbutyl)-N'--phenyl-p-phenylenediamine (K1), 1         part N--(1,4dimethylpentyl)-N'--phenyl-p-phenylenediamine and 4 parts          6ethoxy-2,2,4-trimethyl-1,2-dihydroquinoline (L3)                              (2) 162/3% N--(1,3Dimethylbutyl)-N'--phenyl-p-phenylenediamine (K1),           331/3% N--(1,4dimethylpentyl)-N'-- phenyl-p-phenylenediamine and 50%           6dodecyl-2,2,4-trimethyl-1,2 dihydroquinoline (L2)                             (3) 42% N--(1,3Dimethylbutyl)-N'--phenyl-p-phenylenediamine (K1), 42%          N--(1,4dimethylpentyl)-N'--phenyl-p-phenylenediamine and 16%                   N,N'--bis(1,4dimethylpentyl)-p-phenylenediamine (K8)                     

    8. Mixture of an alkylated mercaptobenzimidazole and an amine                  antioxidant                                                                                            SPECIFIC                                               TRADE NAME  PHYS FORM   GRAVITY   SUPPLIER                                     ______________________________________                                         Stangard 500                                                                               Tan powder  1.24      Harwick                                      ______________________________________                                         9. Amine antioxidant blend-undisclosed composition                                                     SPECIFIC                                               TRADE NAME  PHYS FORM   GRAVITY   SUPPLIER                                     ______________________________________                                         Vanox 200   Brown liquid                                                                               1.13      Vanderbilt                                   Vanox 200 Powder                                                                           Brown powder                                                                               1.40      Vanderbilt                                   ______________________________________                                    

    ______________________________________                                         MISCELLANEOUS UNCLASSIFIED                                                     ANTIOXIDANTS AND ANTIOZONANTS                                                  ______________________________________                                         1. Nickel dibutyldithiocarbamate                                                ##STR83##                                                                     Antiozonant for SBR and NBR antioxidant for several specialty polymers.                                SPECIFIC                                               TRADE NAME  PHYS FORM   GRAVITY   SUPPLIER                                     ______________________________________                                         Akrochem Nibud                                                                             Green solid 1.27      Akron                                                                          Chemical                                     Naugard NBC Green solid 1.27      Uniroyal                                     NBC         Green solid 1.26      duPont                                       Vanox NBC   Green solid 1.27      Vanderbilt                                   ______________________________________                                         2. Nickel diisobutyldithiocarbamate                                             ##STR84##                                                                     Antiozonant for SBR and NBR; antioxidant for several specialty polymers.                               SPECIFIC                                               TRADE NAME  PHYS FORM   GRAVITY   SUPPLIER                                     ______________________________________                                         Isobutyl Niclate                                                                           Green powder                                                                               1.27      Vanderbilt                                   ______________________________________                                         3. Nickel dimethyldithiocarbamate                                               ##STR85##                                                                     Specialty antioxidant and antiozonant.                                                                 SPECIFIC                                               TRADE NAME  PHYS FORM   GRAVITY   SUPPLIER                                     ______________________________________                                         Methyl Niclate                                                                             Green powder                                                                               1.77      Vanderbilt                                   ______________________________________                                         4. 3,9-Bis(3-cyclohexenyl)-2,4,8,10-tetraoxaspiro(5,5)undecane                 Non-staining antiozonant.                                                                              SPECIFIC                                               TRADE NAME  PHYS FORM   GRAVITY   SUPPLIER                                     ______________________________________                                         Vulkanox AFS/LG                                                                            Gray powder 1.06 @    Mobay                                                                90° C.                                          ______________________________________                                         5. Unsaturated acetal absorbed on clay                                         Non-staining antiozonant.                                                                              SPECIFIC                                               TRADE NAME  PHYS FORM   GRAVITY   SUPPLIER                                     ______________________________________                                         Akrochem                                                                       Antiozonant E-9604                                                                         Gray powder 1.74      Akron                                                                          Chemical                                     ______________________________________                                    

The preceding listing of antioxidants is taken from a trade publication entitled: Index of Commercial Antioxidants & Antiozonants, 3rd Edition (1982), distributed by the Goodyear Chemicals division of Goodyear Tire and Rubber Co., Akron, Ohio. That publication does not recommend any of the listed antioxidants specifically for inclusion in polyvinyl chloride compositions, and only recommends the following antioxidants:

N,N'-hexamethylene bis(3,5-di-t-butyl-4-hydroxyhydrocinnamamide);

N,N'-hexamethylene bis(3-(3,5-di-t-butyl-4-hydroxyphenyl)propionamide;

N-stearoyl-p-aminophenol; and

N-(4-hydroxyphenyl)stearamide;

specifically for inclusion in polyamides. (Many of the other listed antioxidants are recommended for inclusion in "plastics" without further definition of a composition.) This index does not suggest inclusion of antimicrobial materials in conjunction with the indicated antioxidants.

SUMMARY OF THE INVENTION

The essence of the present invention resides in the discovery that compositions and articles containing antimicrobial agents can be processed at relatively high temperatures, even when exposing a large surface area to the ambient atmosphere or other sources of oxygen (as when forming films or fibers), if the composition also contains an antioxidant (sometimes referred to herein as a "stabilizer"). Antioxidants have not previously been used to stabilize antimicrobial agents. Both the discovery of the nature of the oxidation problem and the discovery of its solution are facets of the present invention.

One aspect of the invention is an antimicrobial composition having improved resistance to degradation of antimicrobial activity as a result of exposure of said composition to heat. The composition comprises an antimicrobial agent and an antioxidant.

A second aspect of the invention is an unprocessed thermoplastic composition which will be resistant to microbial attack after being processed at an elevated temperature. This composition comprises a resin selected from the group consisting of polypropylene, polyamides, and polyvinyl chloride; an antimicrobial agent; and a amount of an antioxidant effective to reduce degradation of the antimicrobial agent while the composition is being melt processed.

A third aspect of the invention is an article, such as a film or fiber, having resistance to microbial attack. The article comprises a polymeric resin as described in the preceding paragraph, an antimicrobial agent, and an antioxidant. These components are combined to form a composition before the composition is melt processed to form the article.

Method aspects of the invention are also contemplated. One is a method for preserving the efficacy of an antimicrobial agent against heat-induced degradation, comprising the step of adding to the antimicrobial agent an effective amount of an antioxidant. Another is a method for melt processing a composition comprising a thermoplastic resin and an antimicrobial agent while maintaining the efficacy of the antimicrobial agent. This method comprises the steps of combining a thermoplastic resin, an antimicrobial agent, and an antioxidant, followed by melt processing the composition. "Melt processing" means the manipulation of the composition at an elevated temperature, which is typical when forming the composition into a useful article, particularly a fiber or film which has a large surface to volume ratio.

The compositions of the invention have a substantial advantage over unstabilized prior compositions. Either less of the antimicrobial agent can be used to provide a desired level of antimicrobial activity, or a given amount of the antimicrobial agent can provide greater activity.

DETAILED DESCRIPTION OF THE INVENTION

Compositions according to the present invention comprise one part by weight of an antimicrobial agent and from 0.1 to 50 parts, preferably from 1 to 5 parts by weight of an additive referred to here as a "stabilizer" which prevents thermal and oxidative degradation of the antimicrobial agent in the composition.

The contemplated antimicrobial agents stabilized according to the present invention include all those specified in the Background Art section, others known to those of ordinary skill in the art, and mixtures thereof. The preferred antimicrobial agents are as follows:

10,10'-oxybisphenoxarsine (OBPA);

10,10'-oxybisphenarsazine;

bis-n-tributyltin oxide;

zinc Omadine; and

N-(trichloromethylthio)cyclohexenedicarboxamide.

Broadly speaking, the stabilizers contemplated herein can be any material which is stable with respect to the selected antimicrobial agent and under melt processing conditions and which will protect the chosen antimicrobial agent against degradation due to exposure of the composition to heat and oxygen. Epoxidized soybean oil also has utility as an antioxidant.

The preferred antioxidants contemplated herein are selected from the group consisting of: hindered phenols (examples of which are 2,6-di-t-butyl-p-cresol or 2,6-di-t-butyl-4-methylphenol); polyphenols (an example of which is tetrakis(methylene-3-(3,5-di-t-butyl-4-hydroxyhydrocinnamate))methane, sold by Ciba-Geigy Corporation as Irganox 1010; phosphites (an example of which is tris-(2,4-di-t-butylphenyl)phosphite, sold by Ciba-Geigy Corporation, under the trade name Irgafos 168 and as a 1:1 mixture with N,N'-hexamethylene-bis-(3,5-di-t-butyl-4-hydroxyhydrocinnanamide) (Irganox 1098) under the trade name Irganox B 1171); thioesters (e.g. distearyl thiodipropionate); 1,3,5-tris(4-t-butyl-3-hydroxy-2,6-dimethylbenzyl)-s-triazine-2,4,6-(1H,3H,5H)trione; nickel bis(0-ethyl(3,5-di-t-butyl-4-hydroxylbenzyl)phosphonate; zinc 2-mercaptobenzimidazole; aromatic amines (such as N-phenyl-alpha-naphthylamine or alkylated diphenylamines); and combinations of the above.

The synergists contemplated herein are compounds which render the stabilizers more effective, typically by increasing the efficacy of the chosen stabilizer as an antioxidant for the antimicrobial compound. Two exemplary synergists are distearylthiodipropionate (DSTDP) and tris-(2,4-di-t-butylpheyl)phosphite. Other contemplated synergists, which also have utility as antioxidants, are the following compounds

2-mercapto-4-methylbenzimidazole;

2-mercapto-5-methylbenzimidazole;

zinc salt of 2-mercaptobenzimidazole;

2-mercaptotoluimidazole; and

zinc 2-mercaptotoluimidazole.

These are listed as compounds H-1 (2 entries), H-2, H-7, and H-8 in the preceding list of antioxidants. Other synergists known to the art are also contemplated for use herein.

A third ingredient contemplated within the scope of the present invention is a predominant proportion of a polymeric resin, optionally including the usual modifiers and process aids employed in the rubber and plastic formulation arts. Two resin compositions are particularly contemplated herein. First is a concentrate composition containing 1 to 80 percent (all numbers stated herein are by weight unless otherwise indicated) of an antimicrobial agent, a stabilizer, and enough of a polymeric resin to improve the dispersibility of the other ingredients. Second is a composition containing at least about 90% of the resin, preferably from 99 to about 99.99 percent of the resin, and a minor proportion of the antimicrobial agent and its stabilizer. The first composition has utility as a concentrated antimicrobial agent premix which can be readily and uniformly dispersed in a resin composition. The second composition has direct utility as a thermoplastic resin composition for fabrication into useful articles having antimicrobial protection. Other proportions of ingredients are also contemplated.

The resins contemplated for use herein are exemplified by the description in the Background Art section of the specification. Other resins not specified herein are also contemplated within the scope of the invention. The preferred resins are polyamides and polyvinyl chloride, which derive particular benefit from the invention because they are not conventionally compounded with resin antioxidants. Optional resin modifiers contemplated herein include plasticizers; extenders; stabilizers to deter degradation caused by environmental heat and light; fillers; dyes and pigments; flame retardants; lubricants; blowing agents; and so forth. The additives chosen for a particular composition are determined by the desired properties of the final composition. The range of possible additives is limited only by the need to ensure compatibility of all the components of the final composition.

The desired concentrations of the antimicrobial agent and additives in resin compositions are a complex function of the inherent activity of the agent, the tendency toward thermal degradation in other ingredients such as the resin, and the temperature and duration of fabrication. Generally the amount of additive desired is from 0.1 to 50 times, and preferably from about one to about five times the amount of the antimicrobial agent, and the active antimicrobial agent desirably comprises from 0.005% (50 ppm) to 1.0% (10,000 ppm) by weight of the thermoplastic composition. One exemplary unprocessed thermoplastic composition according to the present invention contains from about 170 to about 450 ppm (preferably 220 ppm) of the selected antimicrobial agent and enough of the selected antioxidant that, following heat processing, at least 100 ppm of the active antimicrobial agent will remain. Another exemplary unprocessed thermoplastic composition according to the present invention contains from about 85 to about 220 ppm of the selected antimicrobial agent, and enough of the chosen antioxidant that, after heat processing, at least 50 ppm of the active antimicrobial agent will remain.

It will be appreciated that the ratio: ##EQU1## will depend on the selection of the antimicrobial agent, the identity and amount of the resin and modifiers selected, the processing conditions, and other factors, so no universal ratio can be stated. However, inclusion of an effective antioxidant will always bring the above-stated ratio nearer to its ideal value of 1.0.

In the preferred OBPA composition containing nylon, OBPA, and an amount of an antioxidant sufficient to provide protection during heat processing, the ratio of initial OBPA to final OBPA is about 0.60. Thus, if at least about 100 ppm of OBPA is desired in a fiber, about 170 ppm to about 450 ppm of OBPA is incorporated in the original composition. (If the antioxidant were absent, a final effective level of 100 ppm in nylon fibers would require incorporation of about 500 ppm--three times the level of addition required if the present invention is practiced.) If at least about 50 ppm of OBPA is desired in a fiber, from about 85 to about 220 ppm of OBPA and an effective amount of an antioxidant are incorporated in the composition.

A preferred method for preparing the stabilized plastic compounds is to prepare a blend of the selected resin and antimicrobial agent in which the antimicrobial agent is included in a concentrate as described by Rei in U.S. Pat. No. 4,086,297. The patent is hereby incorporated herein by reference. The blend is then mixed with the desired resin and modifiers.

Compositions specifically contemplated for use herein include those comprising polycaprolactam resin, OBPA as an antimicrobial agent, and a phosphite stabilizer. Nylon is selected because of its desirable properties as a fiber, particularly as a carpet fiber. Nylon fibers are also formed at a high temperature, for example about 285° C. for Nylon 6 (300° C. for Nylon 6,6), and thus antimicrobial agents contained in nylon compositions have previously been substantially or completely inactivated during processing. OBPA is selected because it has a high level of antimicrobial activity, particularly when it is stabilized as taught herein. Phosphite stabilizers are selected because they can protect the microbial agent at the relatively high processing temperature used when fabricating nylon fibers.

Practice of the method inventions taught herein is described or self-evident from the preceding composition description and following examples.

EXAMPLES 1-6

Nylon 6 (polycaprolactam) chips were mixed with processing additives as defined below and with a concentrate of an antimicrobial agent previously prepared according to U.S. Pat. No. 4,086,297 (Rei) to achieve the blend compositions shown

                  TABLE I                                                          ______________________________________                                         Example      1          2        3                                             ______________________________________                                         Polycaprolactam                                                                             99.95%     96.55%   93.45%                                        (fiber grade)                                                                  OBPA         0.05       0.05     0.05                                          Tinuvin 234  --         1.5      1.5                                           Distearylthio-                                                                              --         0.4      0.4                                           dipropionate                                                                   Irganox 1098 --         --       --                                            Irganox B1171                                                                               --         --       --                                            Irganox 1010 --         1.5      --                                            Irganox B215 --         --       4.5                                           Nickel dithio-                                                                              --         --       --                                            carbamate                                                                      Mineral oil  --         --       0.1                                           ______________________________________                                         Example      4          5        6                                             ______________________________________                                         Polycaprolactam                                                                             96.45%     94.95%   96.45%                                        (fiber grade)                                                                  OBPA         0.05       0.05     0.05                                          Tinuvin 234  1.5        1.5      1.5                                           Distearylthio-                                                                              0.4        0.4      0.4                                           dipropionate                                                                   Irganox 1098 1.5        --       --                                            Irganox B1171                                                                               --         3.0      --                                            Irganox 1010 --         --       --                                            Irganox B215 --         --       --                                            Nickel dithio-                                                                              --         --       1.5                                           carbamate                                                                      Mineral Oil  0.1        0.1      0.1                                           ______________________________________                                    

The blend compositions were each extruded into strands approximately 1/16 inch in diameter, cooled in a water bath, and immediately cut into pellets 1/8 inch long. These pellets were then melt-spun into nylon fibers according to techniques commonly known in the industry. The maximum processing temperature was about 285 degrees Celsius.

The fibers were subsequently evaluated for their biological activity by placing each one on a microbiological growth medium, solidified with agar, which had previously been innoculated with an actively growing culture of Staphylococcus aureus.

After incubating the media for 24 hours, the biological activity of each fiber sample was evaluated by measuring the width of the region around the fibers on the agar surface where no visible bacterial growth was evident. This width is defined as a Zone of Inhibition. Another evaluation of biological activity was made by extracting a specimen of each of the test samples with methanol. The extracted material was assayed by high performance liquid chromatography for recovery of the active antimicrobial agent. These results are tabulated in Table II.

                  TABLE II                                                         ______________________________________                                                     Zone of     OBPA                                                   Example     Inhibition (mm)                                                                            % recovered                                            ______________________________________                                         1           3           11                                                     2           5           59                                                     3           7           52                                                     4           6           69                                                     5           5           59                                                     6           5           58                                                     ______________________________________                                    

It will be evident to those skilled in the art that the optimum treatment need not result in 100% recovery of OBPA, since it is added at a very low level and may be unavailable for analysis as the result of incomplete extraction.

These examples show that more undegraded OBPA remains in processed compositions 2-6 which also contain a stabilizing agent, and that the stabilized OBPA of Examples 2-6 is much more microbiocidally active than unstabilized OBPA of Example 1. (It should be understood that the Zone of Inhibition Test is conservative and underestimates the advantage of employing an antioxidant.)

The advantages of the higher active level of an antimicrobial agent resulting from stabilization will be evident to those skilled in the art. For one thing the stabilized fibers can be subjected to a greater amount of post-finishing than unstabilized compositions without reducing the amount or potency of the antimicrobial agent in the fiber when it is put into use.

EXAMPLES 7-10

Unstabilized powdered polypropylene (sold under the trademark Profax 6301 PM by Hercules, Inc., Wilmington, Del.) was mixed with OBPA prepared according to U.S. Pat. No. 4,086,297 and processing additives as follows:

                  TABLE III                                                        ______________________________________                                         Example      7      8           9    10                                        ______________________________________                                         Polypropylene                                                                               99.95  98.70       97.95                                                                               96.95                                     (Profax 6301)                                                                  OBPA          0.05  0.05         0.05                                                                                0.05                                     Irganox 1010 --     1.0         1.0  1.0                                       Distearylthio-                                                                              --     0.25        --   --                                        dipropionate                                                                   Tinuvin 770  --     --          1.0  2.0                                       ______________________________________                                    

The blends were converted into pellets by melt extrusion as in the previous examples. These pellets were melt-spun into polypropylene fibers according to techniques commonly known to the industry.

Microbiological effectiveness and active ingredient levels were obtained as in the previous examples and the results are presented in Table IV.

                  TABLE IV                                                         ______________________________________                                                                    OBPA                                                Example   Zone of Inhibition (mm)                                                                         % Recovered                                         ______________________________________                                         7         0                38                                                  8         7                52                                                  9         7                59                                                  10        6                58                                                  ______________________________________                                    

Again, the fibers of Examples 8-10, which contain a stabilizer for the antimicrobial agent, contain more extractable antimicrobial agent and provide a much greater zone of inhibition than the fiber of Example 7 which contains no stabilizer.

EXAMPLE 11

In this example a polyvinyl chloride film composition containing stabilized OBPA is formed using conventional technology.

The formulation of the base film is:

                  TABLE V                                                          ______________________________________                                         Component            Weight (g)                                                ______________________________________                                         Polyvinyl chloride resin                                                                            100.00                                                    Di-2-ethylexyl phthalate (DOP)                                                                      40.00                                                     Epoxidized soybean oil                                                                              7.70                                                      UV Stabilizer (Mark 202A)                                                                           1.00                                                      Heat Stabilizer (Mark KCB)                                                                          3.50                                                      Heat Stabilizer (Mark C)                                                                            1.50                                                      Stearic Acid         0.25                                                      OBPA concentrate*    .05                                                       ______________________________________                                          *expressed as amount of pure OBPA                                              ("Mark" is a trademark for heat and light stabilizers sold by Argus            Chemical Corp., Brooklyn, New York. DOP is a plasticizer, stearic acid is      a lubricant, and epoxidized soybean oil is an antioxidant.)              

Films are prepared by milling the components of the base until a uniform dispersion is obtained, at which time 0.05% by weight of carbon black is added.

The film is extrusion cast using conventional equipment at a processing temperature of 375 degrees Fahrenheit (191 degrees Celsius). The final film has a thickness of about 20 mils (500 microns). A control film is made in the same manner except that the stabilizer is omitted. The microbiocidal activity of the film is measured by cutting small round pieces of the test and control films, placing each one on an innoculated growth medium as described in Examples 1-6, and proceeding as described in those examples to develop and measure a Zone of Inhibition. The test samples are then extracted with methanol and the amount of recovered active ingredient is measured as described in Examples 1-6. Results comparable to those set forth in Examples 1-6 are obtained, illustrating that the invention can be used to improve antimicrobial films.

EXAMPLE 12

Examples 1 and 2 are repeated, except the OBPA is replaced in separate trials by each of the antimicrobial agents specified in the Background Art section of the present specification. The compositions analogous to Example 2 show much greater antimicrobial activity and a much greater recovery of the active antimicrobial agent than the corresponding compositions analogous to Example 1. This illustrates the applicability of the invention to each of the named antimicrobial agents.

EXAMPLE 13

Examples 1 and 2 are repeated, except the antioxidant (Irganox 1010) of Example 2 is replaced, in separate trials, by each of the antioxidants set forth in the Background Art section of the present specification. The compositions analogous to Example 2 show much greater antimicrobial activity and a much greater recovery of the active antimicrobial agent than the corresponding compositions analogous to Example 1. Thus, a wide range of antioxidants can be used to practice the invention.

EXAMPLE 14

Examples 1 and 2 are repeated, replacing polycaprolactam with each of the resins specified in the Background Art section of the present application in separate trials. Similar results are again obtained, and show the value of the invention for improving the antimicrobial properties of many different resin compositions.

EXAMPLE 15

The following test composition was blended and formed into test fibers according to the procedure described in Examples 1-6:

    ______________________________________                                         Ingredient       Wt. %                                                         ______________________________________                                         polycaprolactam  98.96                                                         Irganox B1171    0.50                                                          Tinuvin T234     0.50                                                          OBPA             0.04                                                          Total            100.00                                                        ______________________________________                                    

The fibers were then subjected to a modified continuous dyeing process adapted to simulate commercial continuous dyeing processes. The fibers were wet with a 0.1% by weight aqueous solution of a nonionic surfactant sold under the trademark Alrowet by Ciba-Geigy Corporation, Dyestuffs and Chemicals Division, Greensboro N.C.; followed by an aliquot of an aqueous solution adjusted to a pH value of 6.0 and containing 0.1% of the same surfactant and 2% of a dye sold under the trademark "Tectilon Blue 4RKWL" by Ciba-Geigy Corporation, Dyestuffs and Chemicals Division, Greensboro, N.C. The saturated fibers were steamed for 360 seconds at 101° C. and atmospheric pressure, followed by three rinses, each one liter of 40° C. tap water.

Fibers so treated were found to have retained all of their antimicrobial potency and 76% of their OBPA, as measured by high performance liquid chromatography.

EXAMPLE 16

Test fibers like those of Example 15 were used again here. A control composition lacking Irganox B1171 antioxidant but otherwise containing the same ingredients in the same proportions was processed in the same manner, then formed into control fibers.

The test and control fibers were then subjected to Beck mock-dyeing. Mock dye baths were prepared having a pH of 4.0 and containing 0.1% Triton X-100 surfactant in aqueous solution. In separate trials, 5% and 10% (based on the weight of the dye bath) of the test and control fibers were added to the boiling dye baths. The dye baths were boiled for up to 30 minutes.

The baths were then analyzed for arsenic content. The baths used to boil the control fibers contained about three times as much arsenic as the corresponding baths used to boil the test fibers containing an antioxidant. Thus, use of an antioxidant to preserve an antimicrobial agent in these fiber compositions reduces the loss of decomposition products of the antimicrobial agent into the dye bath, and thus into the dye effluent. 

What is claimed is:
 1. A thermoplastic composition which will be resistant to microbial attack after being processed at an elevated temperature, comprising a homogeneous mixture of:A. a polyamide resin; B. an antimicrobial agent; and C. an amount of an antioxidant effective to reduce degradation of said antimicrobial agent while said composition is being melt-processed.
 2. The composition of claim 1, wherein said antioxidant is at least one member selected from the group consisting of:monophenols; bisphenols thiobisphenols; polyphenols; hydroquinones; phosphites; thioesters; naphthylamines; diarylamines; p-phenylenediamines; quinolines; blended amines; 0,0-di-n-octadecyl(3,5-di-t-butyl-4-hydroxybenzyl)phosphonate); 1,6-hexamethylene bis(3,5-di-t-butyl-4-hydroxyhydrocinnamate); 1,6-hexamethylene bis(3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate); thiodiethylene bis(3,5-di-t-butyl-4-hydroxy)hydrocinnamate; thiodiethylene bis(3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate); octadecyl-3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate; octadecyl-3,5-di-t-butyl-4-hydroxyhydrocinnamate;
 3. 3. 5-di-t-butyl-4-hydroxyhydrocinnamic acid triester with 1,3,5-tris (2-hydroxyethyl)-s-triazine-2,4,6-(1H,3H,5H)trione;N-butyryl-p-aminophenol; N-(4-hydroxyphenyl)butyramide; N-pelargonoyl-p-aminophenol; N-(4-hydroxyphenyl)pelargonamide; N-lauroyl-p-aminophenol; N-(4-hydroxyphenyl)dodecanamide; 2,6-di-t-butyl-alpha-dimethylamino-p-cresol; 2,6-di-t-butyl-4-(dimethylaminomethyl)phenol; 1,3,5-tris(4-t-butyl-3-hydroxy-2,6-dimethylbenzyl)-s-triazine-2,4,6-(1H,3H,5H)trione; nickel bis(0-ethyl(3,5-di-butyl-4-hydroxybenzyl)phosphonate); 2,2'-oxamidobisethyl-3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate; tris(2-t-butyl-4-(2-methyl-4-hydroxy-5-t-butylphenylthio)-5-methyl)-phenylphosphite; bis(3,3-bis(4-hydroxy-3-t-butylphenyl)butanoic acid glycolester; tetrakis(2,4-di-t-butylphenyl)-4,4'-biphenylylenediphosphonite; n-propyl gallate; n-propyl-3,4,5-trihydroxybenzoate; calcium bis(0-ethyl(3,5-di-t-butyl-4-hydroxybenzyl)phosphonate); 2-mercapto-4-methylbenzimidazole; 2-mercapto-5-methylbenzimidadole; zinc salt of 2-mercaptobenzimidazole; 2-mercapto-4-methylbenzimidazole, zinc salt; 2-mercapto-5-methylbenzimidazole, zinc salt; 2-mercaptotoluimidazole; zinc 2-mercaptotoluimidazole; dioctadecyl disulfide; metal aromatic sulfonates; nickel di-n-butyldithiocarbamate; nickel diisobutyldithiocarbamate; nickel dimethyldithiocarbamate; 3,9-bis(3-cyclohexenyl)-2,4,8,10-tetraoxaspiro(5,5)undecane; and tris (5-norbornene-2-methyl)phosphite.
 3. The composition of claim 1, wherein said antioxidant is 2,6-di-t-butyl-p-cresol.
 4. The composition of claim 1, wherein said antioxidant is 2,6-di-t-butyl-4-methylphenol.
 5. The composition of claim 1, wherein said antioxidant is tetrakis(methylene-3-(3,5-di-t-butyl-4-hydroxyhydrocinnamate))methane.
 6. The composition of claim 1, wherein said antioxidant is tris-(2,4-di-t-butylphenyl)phosphite.
 7. The composition of claim 1, wherein said antioxidant is distearyl thiodipropionate.
 8. The composition of claim 1, wherein said antioxidant is 1,3,5-tris(4-t-butyl-3-hydroxy-2,6-dimethylbenzyl)-s-triazine-2,4,6-(1H,3H,5H)trione.
 9. The composition of claim 1 wherein said antioxidant is nickel bis(O-ethyl(3,5-di-t-butyl-4-hydroxylbenzyl)phosphonate).
 10. The composition of claim 1, wherein said antioxidant is zinc 2-mercaptobenzimidazole.
 11. The composition of claim 1, wherein said antioxidant is N-phenyl-alpha-naphthylamine.
 12. The composition of claim 1, wherein said antioxidant is an alkylated diphenylamine.
 13. The composition of claim 1, wherein said antioxidant is N,N'-hexamethylene bis(3,5-di-t-butyl-4-hydroxyhydrocinnamamide).
 14. The composition of claim 1, wherein said antioxidant is N,N'-hexamethylene bis(3-(3,5-di-t-butyl-4-hydroxyphenyl)propionamide.
 15. The composition of claim 1, wherein said antioxidant is 1,6-hexamethylene bis-(3,5-di-t-butyl-4-hydroxyhydrocinnamide).
 16. The composition of claim 1, wherein said antioxidant is tetrakis(methylene 3,5-di-t-butyl-4-hydroxyphenyl propionate)methane.
 17. The composition of claim 1, wherein said antioxidant is tetrakis(methylene-3,5-di-t-butyl-4-hydroxyhydrocinnamate)methane.
 18. The composition of claim 1, wherein said antioxidant is nickel dithiocarbamate.
 19. The composition of claim 1, wherein said resin is polycaprolactam.
 20. The composition of claim 1, wherein said antimicrobial agent comprises from about 170 to about 450 ppm of 10,10'-oxybisphenoxarsine, and provides an active level of 10,10'-oxybisphenoxarsine of at least about 100 ppm after said processing at an elevated temperature.
 21. The composition of claim 1, wherein said antimicrobial agent comprises from about 85 to about 220 ppm of 10,10'-oxybisphenoxarsine, and provides an active level of 10,10'-oxybisphenoxarsine of at least 50 ppm after said processing at an elevated temperature.
 22. The composition of claim 20, wherein said antimicrobial agent comprises about 170 ppm thereof.
 23. The composition of claim 20, wherein said antimicrobial agent comprises about 200 ppm thereof.
 24. The composition of claim 1, wherein said antimicrobial agent is 10,10'-oxybisphenoxarsine, said antioxidant is at least one member selected from the group consisting of:distearyldithiopropionate; N,N'-hexamethylene bis(3,5-di-t-butyl-4-hydroxyhydrocinnamamide); N,N'-hexamethylene bis(3,5-di-t-butyl-4-hydroxyhydrocinnamide); 1,6-hexamethylene bis-(3,5-di-t-butyl-4hydroxyhydrocinnamide); tris-(2,4-di-t-butylphenyl)phosphite; tetrakis(methylene-3-(3,5-di-t-butyl-4-hydroxyhydrocinnamate))methane; and nickel dithiocarbamate;and said resin is polycaprolactam.
 25. The composition of claim 24, wherein said 10,10'-oxybisphenoxarsine comprises from about 170 to about 450 ppm thereof, and provides an active level of said 10,10'-oxybisphenoxarsine of at least about 100 ppm after said processing at an elevated temperature.
 26. The composition of claim 24, wherein said 10,10'-oxybisphenoxarsine comprises from about 85 to about 220 ppm thereof and provides an active level of said 10,10'-oxybisphenoxarsine of at least 50 ppm after said processing at an elevated temperature.
 27. The composition of claim 24, wherein said 10,10'-oxybisphenoxarsine comprises about 170 ppm thereof.
 28. The composition of claim 24, wherein said 10,10'-oxybisphenoxarsine comprises about 200 ppm thereof.
 29. An article selected from the group consisting of fibers and films, said article having resistance to microbial attack, said article comprising a homogeneous mixture of:A. a polyamide resin; B. an antimicrobial agent; and C. an antioxidant;wherein said ingredients A, B, and C are combined to form a composition before said composition is melt-processed to form said article.
 30. The article of claiim 29, wherein said antioxidant is at least one member selected from the group consisting of:monophenols; bisphenols; thiobisphenols; polyphenols; hydroquinones; phosphites; thioesters; naphthylamines; diarylamines; p-phenylenediamines; quinolines; blended amines; O,O-di-n-octadecyl(3,5-di-t-butyl-4-hydroxybenzyl)phosphonate;
 1. 6-hexamethylene bis(3,5-di-t-butyl-4-hydroxyhydrocinnamate;1,6-hexamethylene bis(3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate); thiodiethylene bis(3,5-di-t-butyl-4-hydroxy)hydrocinnamate; thiodiethylene bis(3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate); octadecyl-3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate; octadecyl-3,5-di-t-butyl-4-hydroxyhydrocinnamate; 3,5-di-t-butyl-4-hydroxyhydrocinnamic acid triester with 1,3,5-tris(2-hydroxyethyl)-s-triazine-2,4,6-(1H,3H,5H)trione; N-butyryl-p-aminophenol; N-(4-hydroxyphenyl)butyramide; N-pelargonoyl-p-aminophenol; N-(4-hydroxyphenyl)pelargonamide; N-lauroyl-p-aminophenol; N-(4-hydroxyphenyl)dodecanamide; 2,6-di-t-butyl-alpha-dimethylamino-p-cresol; 2,6-di-t-butyl-4-(dimethylaminomethyl)phenol; 1,3,5-tris(4-t-butyl-3-hydroxy-2,6-dimethylbenzyl)-s-triazine-2,4,6-(1H,3H,5H)trione; nickel bis(0-ethyl(3,5-di-t-butyl-4-hydroxybenzyl)phosphonate);
 2. 2'-oxamidobisethyl-3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate;tris(2-t-butyl-4-(2-methyl-4-hydroxy-5-t-butylphenylthio)-5-methyl)-phenylphosphite; bis(3,3-bis(4-hydroxy-3-t-butylphenyl)butanoic acid glycolester; tetrakis(2,4-di-t-butylphenyl)-4,4'-biphenylylenediphosphonite; n-propyl gallate; n-propyl-3,4,5-trihydroxybenzoate; calcium bis(0-ethyl(3,5-di-t-butyl-4-hydroxybenzyl)phosphonate); 2-mercapto-4-methylbenzimidazole; 2-mercapto-5-methylbenzimidazole; zinc salt of 2-mercaptobenzimidazole; 2-mercapto-4-methylbenzimidazole, zinc salt; 2-mercapto-5-methylbenzimidazole, zinc salt; 2-mercaptotoluimidazole; zinc-2-mercaptotoluimidazole; dioctadecyl disulfide; metal aromatic sulfonates; nickel di-n-butyldithiocarbamate; nickel diisobutyldithiocarbamate; nickel dimethyldithiocarbamate; 3,9-bis(3-cyclohexenyl)-2,4,8,10-tetraoxaspiro(5,5)undecane; and tris(5-norbornene-2-methyl)phosphite.
 31. The article of claim 30, wherein said resin is polycaprolactam.
 32. The article of claim 29, wherein said antimicrobial agent is 10,10'-oxybisphenoxarsine, said antioxidant is at least one member selected from the group consisting of:distearyldithiopropionate; N,N'-hexamethylene bis(3,5-di-t-butyl-4-hydroxyhydrocinnamamide); N,N'-hexamethylene bis(3-(3,5-di-t-butyl 4-hydroxyphenyl)propionamide); 1,6-hexamethylene bis-(3,5-di-t-butyl-4-hydroxyhydrocinnamide); tris-2(2,4-di-t-butylphenyl)phosphite; tetrakis(methylene-3-(3,5-di-t-butyl-4-hydroxyhydrocinnamate)methane; and nickel dithiocarbamate;and said resin is polycaprolactam.
 33. The composition of claim 1, wherein the weight ratio of said antimicrobial agent to said stabilizer is from about 1:1 to about 1:5.
 34. The composition of claim 24, wherein the weight ratio of said antimicrobial agent to said stabilizer is from about 1:1 to about 1:5.
 35. A thermoplastic composition which will be resistant to microbial attack after being processed at an elevated temperature, comprising a homogeneous mixture of:A. a resin selected from the group consisting of polypropylene, polyamide, and polyvinyl chloride; B. an antimicrobial agent; and C. an amount of an antioxidant effective to reduce degradation of said antimicrobial agent while said composition is being melt processed, wherein said antioxidant is at least one member selected from the group consisting of:hydroquinones; thioesters; naphthylamines; diarylamines; p-phenylenediamines; quinolines; blended amines; tetrakis(2,4-di-t-butylphenyl)-4,4'-biphenylylenediphosphonite; 2-mercapto-4-methylbenzimidazole; 2-mercapto-5-methylbenzimidazole; zinc salt of 2-mercaptobenzimidazole; 2-mercapto-4-methylbenzimidazole, zinc salt; 2-mercapto-5-methylbenzimidazole, zinc salt; 2-mercaptotoluimidazole; zinc 2-mercaptotoluimidazole; dioctadecyl disulfide; metal aromatic sulfonates; nickel di-n-butyldithiocarbamate; nickel diisobutyldithiocarbamate; nickel dimethyldithiocarbamate; and 3,9-bis(3-cyclohexenyl)-2,4,8,10-tetraoxaspiro(5,5)undecane.
 36. The composition of claim 35, wherein said antioxidant is distearyl thiodipropionate.
 37. The composition of claim 35, wherein said antioxidant is zinc 2-mercaptobenzimidazole.
 38. The composition of claim 35, wherein said antioxidant is N-phenyl-alpha-naphthylamine.
 39. The composition of claim 35, wherein said antioxidant is an alkylated diphenylamine.
 40. The composition of claim 35, wherein said antioxidant is nickel dithiocarbamate.
 41. The composition of claim 35, wherein said resin is a polyamide.
 42. The composition of claim 35, wherein said resin is polycaprolactam.
 43. The composition of claim 35, wherein said antimicrobial agent comprises from about 170 to about 450 ppm of 10,10'-oxybisphenoxarsine, and provides an active level of 10,10'-oxybisphenoxarsine of at least about 100 ppm after said processing at an elevated temperature.
 44. The composition of claim 43, wherein said antimicrobial agent comprises about 170 ppm thereof.
 45. The composition of claim 43, wherein said antimicrobial agent comprises about 200 ppm thereof.
 46. The composition of claim 35, wherein said antimicrobial agent comprises from about 85 to about 220 ppm of 10,10'-oxybisphenoxarsine, and provides an active level of 10,10'-oxybisphenoxarsine of at least 50 ppm after said processing at an elevated temperature.
 47. The composition of claim 35, wherein the weight ratio of said antimicrobial agent to said stabilizer is from about 1:1 to about 1:5.
 48. The composition of claim 35, wherein said antimicrobial agent is 10,10'-oxybisphenoxarsine, said antioxidant is at least one member selected from the group consisting of:distearyldithiopropionate; and nickel dithiocarbamate;and said resin is polycaprolactam.
 49. The composition of claim 48, wherein the weight ratio of said antimicrobial agent to said stabilizer is from about 1:1 to about 1:5.
 50. An article selected from the group consisting of fibers and films, said article having resistance to microbial attack, said article comprising a homogeneous mixture of:A. a polymeric resin selected from the group consisting of polyamides, polyvinyl chlorides and polypropylene; B. an antimicrobial agent; and C. an antioxidant;wherein said ingredients A, B, and C are combined to form a composition before said composition is meltprocessed to form said article, and wherein said antioxidant is at least one member selected from the group consisting of: hydroquinones; thioesters; naphthylamines; diarylamines; p-phenylenediamines; quinolines; blended amines; tetrakis(2,4-di-t-butylphenyl)-4,4'-biphenylylenediphosphonite; 2-mercapto-4-methylbenzimidazole; 2-mercapto-5-methylbenzimidazole; zinc salt of 2-mercaptobenzimidazole; 2-mercapto-4-methylbenzimidazole, zinc salt; 2-mercapto-5-methylbenzimidazole, zinc salt; 2-mercaptotoluimidazole; zinc-2-mercaptotoluimidazole; dioctadecyl disulfide metal aromatic sulfonates; nickel di-n-butyldithiocarbamate; nickel diisobutyldithiocarbamate; nickel dimethyldithiocarbamate; and 3,9-bis(3-cyclohexenyl)-2,4,8,10-tetraoxaspiro(5,5)undecane.
 51. The article of claim 50, wherein said resin is a polyamide.
 52. The article of claim 51, wherein said resin is polycaprolactam.
 53. The article of claim 50, wherein said antimicrobial agent is 10,10'-oxybisphenoxarsine, said antioxidant is at least one member selected from the group consisting of:distearyldithiopropionate; and nickel dithiocarbamate;and said resin is polycaprolactam.
 54. A method for melt processing a composition comprising a thermoplastic resin and an antimicrobial agent while maintaining the efficacy of said agent, comprising the following steps performed in the order stated:A. combining said thermoplastic resin, said antimicrobial agent, and an antioxidant to form a protected antimicrobial resin composition; and B. melt processing said protected antimicrobial resin composition.
 55. A method for providing a desired final active level of at least 1 part by weight of 10,10'-oxybisphenoxarsine in a composition following heat processing thereof, comprising the steps of:A. providing a thermoplastic composition comprising a major proportion of a resin selected from the group consisting of polypropylene, polyamide, and polyvinyl chloride; about 1.7 parts by weight of 10,10'-oxybisphenoxarsine; and from about 1.7 to about 8.5 parts by weight of an antioxidant; and B. processing said composition at a temperature of at lest about 275 degrees Celsius;thereby providing a heat-processed composition containing at least about 1.0 parts by weight of said 10,10'-oxybisphenoxarsine in active form.
 56. The method of claim 55, wherein said resin is a polyamide resin.
 57. The method of claim 55, wherein said processing step is carried out by melt processing said thermoplastic composition to form an article selected from the group consisting of fibers and films.
 58. The method of claim 57, comprising the subsequent step of vat dyeing said article.
 59. The method of claim 58, wherein said article is a carpet fiber.
 60. A method for melt-processing a composition comprising a thermoplastic polyamide resin and an antimicrobial agent while maintaining the efficacy of said agent, comprising the following steps performed in the order stated:A. combining said thermoplastic polyamide resin, said antimicrobial agent, and an antioxidant homogeneously to form a protected antimicrobial resin composition; and B. melt-processing said protected antimicrobial resin composition.
 61. A method for providing a desired final active level of at least 1 part by weight of 10,10'-oxybisphenoxarsine in a composition following heat processing thereof, comprising the steps of:A. providing a thermoplastic composition comprising about 1.7 parts by weight of 10,10'-oxybisphenoxarsine, from about 1.7 to about 8.5 parts by weight of an antioxidant, and a major proportion of a polyamide resin; and B. processing said thermoplastic composition at a temperature of at least about 275 degreess Celsius;thereby providing a heat-processed composition containing about 1.0 parts by weight of said 10,10'-oxybisphenoxarsine in active form.
 62. The method of claim 61, wherein said processing step is carried out by melt processing said thermoplastic composition to form an article selected from the group consisting of fibers and films.
 63. The method of claim 62, comprising the subsequent step of vat dyeing said article.
 64. The method of claim 63, wherein said article is a carpet fiber. 